WO2020080067A1 - Précurseur de plaque d'impression planographique et procédé de production de plaque d'impression planographique - Google Patents

Précurseur de plaque d'impression planographique et procédé de production de plaque d'impression planographique Download PDF

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Publication number
WO2020080067A1
WO2020080067A1 PCT/JP2019/038262 JP2019038262W WO2020080067A1 WO 2020080067 A1 WO2020080067 A1 WO 2020080067A1 JP 2019038262 W JP2019038262 W JP 2019038262W WO 2020080067 A1 WO2020080067 A1 WO 2020080067A1
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Prior art keywords
printing plate
group
lithographic printing
plate precursor
formula
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PCT/JP2019/038262
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English (en)
Japanese (ja)
Inventor
加奈 栢木
尚志 佐藤
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富士フイルム株式会社
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Publication of WO2020080067A1 publication Critical patent/WO2020080067A1/fr

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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
    • B41N1/00—Printing plates or foils; Materials therefor
    • B41N1/12—Printing plates or foils; Materials therefor non-metallic other than stone, e.g. printing plates or foils comprising inorganic materials in an organic matrix
    • B41N1/14—Lithographic printing foils
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/32—Liquid compositions therefor, e.g. developers

Definitions

  • the present disclosure relates to a lithographic printing plate precursor and a method for producing a lithographic printing plate.
  • 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, and the lipophilic image part of the lithographic printing plate is the ink receiving part, and the hydrophilic non-image part is the dampening water receiving part (ink non-receiving part).
  • image exposure is performed by a CTP (computer to plate) technique. That is, image exposure is carried out by using a laser or a laser diode directly on a lithographic printing plate precursor by scanning exposure without using a lith film.
  • a conventional lithographic printing plate precursor or a photosensitive resin composition used for manufacturing the same for example, those described in Patent Documents 1 and 2 are known.
  • Patent Document 1 discloses a lithographic printing plate precursor comprising a support and a resin and an infrared absorbing agent, and having at least two or more positive type recording layers whose solubility in an alkaline aqueous solution is increased by infrared laser exposure, on a support, Of the positive recording layers, the positive recording layer closest to the support contains at least two resins, at least one of these resins forms a dispersed phase, and at least one of the above resins is used.
  • a lithographic printing plate precursor characterized in that one is a polymer containing maleimide is described.
  • Patent Document 2 an image recording layer containing a ternary to quaternary copolymer having a maleimide structure and an infrared absorber is provided on a support, and the weight average molecular weight of the above copolymer is 15,000 to 35. And a lithographic printing plate precursor having a number average molecular weight of 7,000 to 15,000.
  • Patent Document 1 Japanese Patent Laid-Open No. 2006-3658
  • Patent Document 2 Chinese Patent Application Publication No. 1038716969
  • the problem to be solved by the embodiments of the present invention is to provide a lithographic printing plate precursor which is excellent in post-exposure aging developability.
  • a problem to be solved by another embodiment of the present invention is to provide a method for producing a lithographic printing plate using the lithographic printing plate precursor.
  • Means for solving the above problems include the following aspects. ⁇ 1> An alkali-soluble resin having an image recording layer on a support, the image recording layer having a structural unit represented by the following formula (1) and a structural unit having a phenolic hydroxyl group in a side chain, infrared absorption A lithographic printing plate precursor comprising an agent and a sulfonium salt compound represented by the following formula (S).
  • R represents an alkyl group or an aryl group.
  • R 1 to R 3 each independently represents an alkyl group having 20 or less carbon atoms or an aryl group having 20 or less carbon atoms
  • X ⁇ is a sulfonate ion, a carboxylate ion, or a halogen atom.
  • At least one aromatic ring in the above triarylsulfonium salt compound is a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, and an aryl having 12 or less carbon atoms.
  • the lithographic printing plate precursor as described in ⁇ 2> which has at least one group selected from the group consisting of oxy groups.
  • ⁇ 4> The lithographic printing plate precursor as described in any one of ⁇ 1> to ⁇ 3>, wherein X ⁇ in the sulfonium salt compound has an aromatic group.
  • ⁇ 5> The lithographic printing plate precursor as described in any one of ⁇ 1> to ⁇ 4>, wherein X ⁇ in the sulfonium salt compound has a phenolic hydroxyl group.
  • ⁇ 6> The lithographic printing plate precursor as described in any one of ⁇ 1> to ⁇ 5>, wherein X ⁇ in the sulfonium salt compound has a diarylketone structure.
  • ⁇ 7> The lithographic printing plate precursor as described in any one of ⁇ 1> to ⁇ 6>, in which the image recording layer has an upper layer and a lower layer.
  • ⁇ 8> The lithographic printing plate precursor as described in ⁇ 7>, wherein the upper layer contains the infrared absorbent and the sulfonium salt compound, and the lower layer contains the alkali-soluble resin.
  • ⁇ 9> The lithographic printing plate precursor as described in any one of ⁇ 1> to ⁇ 8>, which is a lithographic printing plate precursor for non-silicate development.
  • the solution activity of the alkali developer is measured by the conductivity of the alkali developer, and a replenisher is added according to the measured value to adjust the solution activity to a target conductivity to control the solution activity.
  • the method for producing a lithographic printing plate as described in ⁇ 10> which comprises the step of:
  • lithographic printing plate precursor that is excellent in post-exposure aging developability. Further, according to another embodiment of the present invention, it is possible to provide a method for producing a planographic printing plate using the planographic printing plate precursor.
  • FIG. 3 is a schematic view of an electrolytic treatment apparatus in a two-stage power supply electrolysis method applicable to production of a support.
  • the amount of each component in the composition is the total amount of the corresponding plurality of substances present in the composition, unless a plurality of substances corresponding to each component are present in the composition.
  • the notation that does not indicate substituted and unsubstituted includes not only those having no substituent but also those having a substituent.
  • the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • (meth) acrylic is a term used as a concept including both acryl and methacryl
  • (meth) acryloyl is a term used as a concept including both acryloyl and methacryloyl. is there.
  • the group in the compound represented by the formula when no substitution or substitution is mentioned, and when the group can further have a substituent, there is no particular limitation. As long as the group includes not only an unsubstituted group but also a group having a substituent.
  • R V represents an alkyl group, an aryl group or a heterocyclic group
  • R V is an unsubstituted alkyl group, a substituted alkyl group, an unsubstituted aryl group, a substituted aryl group
  • process in the present disclosure is included in this term as long as the intended purpose of the process is achieved, not only when it is an independent process but also when it cannot be clearly distinguished from other processes. Be done.
  • “mass%” and “weight%” are synonymous, and “mass part” and “weight part” are synonymous.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) in the present disclosure are columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (both manufactured by Tosoh Corporation) unless otherwise specified.
  • the gel permeation chromatography (GPC) analyzer was used to detect the solvent THF (tetrahydrofuran) with a differential refractometer, and the molecular weight was calculated using polystyrene as a standard substance.
  • the total solid content refers to the total mass of components excluding volatile components such as a solvent in the composition.
  • 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 through an operation such as exposure and development, but also a discarding 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 lithographic printing plate precursor to be attached to an unused plate cylinder when a part of the paper surface is printed in a single color or two colors in color newspaper printing, for example.
  • the lithographic printing plate precursor according to the present disclosure has an image recording layer on a support, and the image recording layer comprises a structural unit represented by the following formula (1) and a structural unit having a phenolic hydroxyl group in a side chain. It contains an alkali-soluble resin, an infrared absorber, and a sulfonium salt compound represented by the following formula (S).
  • R represents an alkyl group or an aryl group.
  • R 1 to R 3 each independently represents an alkyl group having 20 or less carbon atoms or an aryl group having 20 or less carbon atoms
  • X ⁇ is a sulfonate ion, a carboxylate ion, or a halogen atom.
  • the lithographic printing plate precursor according to the present disclosure is a positive lithographic printing plate precursor, and preferably a thermal positive lithographic printing plate precursor. Furthermore, the lithographic printing plate precursor according to the present disclosure can be suitably used as a lithographic printing plate precursor for non-silicate development.
  • an alkali-soluble resin having a structural unit represented by the above formula (1) and a structural unit having a phenolic hydroxyl group (also referred to as “phenolic hydroxy group”) in a side chain and the above formula (S ) Is used in combination with the sulfonium salt compound, the maleimide ring structure and the phenolic hydroxyl group in the alkali-soluble resin and the sulfonium salt compound interact with each other. It is presumed that the difference in solubility with respect to the parts is maintained and the developability (post-exposure aging developability) is excellent even when the lithographic printing plate precursor is stored after exposure.
  • the image recording layer contains the alkali-soluble resin and the sulfonium salt compound represented by the formula (S), so that they are bonded by hydrogen bond and ionic bond. Since they interact with each other, the difference in solubility between the exposed area and the non-exposed area becomes larger, and it is presumed that the image recording layer has excellent development latitude (acceptance of development conditions suitable for image formation).
  • S the alkali-soluble resin
  • S sulfonium salt compound represented by the formula (S)
  • the image recording layer in the lithographic printing plate precursor according to the present disclosure includes an alkali-soluble resin having a structural unit represented by the above formula (1) and a structural unit having a phenolic hydroxyl group in a side chain, an infrared absorber, and the above formula.
  • a sulfonium salt compound represented by (S) is included.
  • the image recording layer has an alkali-soluble resin (simply “alkali-soluble resin”) having a structural unit represented by the above formula (1) and a structural unit having a phenolic hydroxyl group in a side chain. Also referred to as).
  • alkali-soluble resin in the present disclosure means being soluble in a 1 mol / L sodium hydroxide solution at 25 ° C. Further, “soluble” means that 0.1 g or more is dissolved in 100 mL of solvent.
  • the alkali-soluble resin is preferably a copolymer obtained by copolymerizing at least a maleimide compound and a (meth) acrylic compound or a styrene compound, and at least a maleimide compound and a (meth) acrylamide compound are copolymerized. It is more preferable that the copolymer is
  • the alkali-soluble resin has a structural unit represented by the following formula (1).
  • the constitutional unit represented by the following formula (1) is preferably a constitutional unit derived from a maleimide compound (a constitutional unit obtained by copolymerizing a maleimide compound).
  • R represents an alkyl group or an aryl group.
  • the alkyl group and aryl group for R in formula (1) may have a substituent.
  • substituents include an alkyl group, an aryl group, a halogen atom, a hydroxy group, an alkoxy group, a carboxy group, an alkoxycarbonyl group, an acyl group, an acyloxy group and a cyano group.
  • the above-mentioned substituent may further have a substituent.
  • the number of carbon atoms (also referred to as “carbon number”) of the alkyl group represented by R in the formula (1) is preferably 1 to 20, more preferably 1 to 12, and further preferably 1 to 8. More preferable.
  • the number of carbon atoms of the alkyl group represented by R in the formula (1) is preferably 2 or more from the viewpoint of development latitude.
  • the aryl group represented by R in the formula (1) preferably has 6 to 20 carbon atoms, more preferably has 6 to 12 carbon atoms, and further preferably has 6 to 10 carbon atoms.
  • the aryl group represented by R in the formula (1) may be an aryl group having a monocyclic structure or an aryl group having a structure in which two or more rings are condensed.
  • R in the formula (1) is preferably an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms from the viewpoint of developability with time after exposure, and has 1 to 12 carbon atoms.
  • a group, a benzyl group, or a phenyl group is particularly preferable, and a phenyl group is most preferable.
  • R in the formula (1) is preferably an aryl group from the viewpoint of development latitude and post-exposure aging developability.
  • alkyl group represented by R in the formula (1) examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a s-butyl group, a t-butyl group, a cyclohexyl group and a benzyl group.
  • aryl group for R in the formula (1) include a phenyl group and a naphthyl group.
  • Examples of the monomer forming the structural unit represented by the formula (1) include N-methylmaleimide, Nn-butylmaleimide, N-benzylmaleimide, N-phenylmaleimide, N-naphthylmaleimide and the like. The disclosure is not limited to these.
  • constitutional unit represented by the formula (1) are preferably the followings.
  • the alkali-soluble resin may have one type of the structural unit represented by the above formula (1) alone, or may have two or more types. From the viewpoint of development latitude and post-exposure aging developability, the content of the constitutional unit represented by the above formula (1) (the total content in the case of two or more kinds, the same applies hereinafter) is the same as that of the alkali-soluble resin.
  • the amount is preferably 10 mol% to 80 mol%, more preferably 10 mol% to 60 mol%, particularly preferably 20 mol% to 55 mol%.
  • the “constituent unit” is synonymous with the “monomer unit”.
  • the “monomer unit” may be modified after polymerization by a polymer reaction or the like. The same applies to the following.
  • the alkali-soluble resin has a structural unit having a phenolic hydroxyl group on its side chain.
  • the “main chain” represents the relatively longest binding chain in the molecule of the polymer compound constituting the resin
  • the “side chain” represents the atomic group branched from the main chain.
  • the number of phenolic hydroxyl groups contained in the constituent unit having a phenolic hydroxyl group in the side chain is not particularly limited, but is preferably 1 to 4 from the viewpoint of developability and development latitude, and 1 or 2 It is more preferable that the number is 1, and it is particularly preferable that the number is 1.
  • the structure having a phenolic hydroxyl group in the structural unit having a phenolic hydroxyl group in the side chain preferably has a nitrogen atom from the viewpoint of development latitude and post-exposure developability after exposure, and is represented by the following formula (Ph-1). It is more preferable that the structure is
  • R ph1 each independently represent a monovalent substituent
  • R ph2 represents a hydrogen atom, an alkyl group or an aryl group
  • n1 represents an integer of 1 ⁇ 4
  • n2 is It represents an integer of 0 to 4
  • the wavy line represents the bonding position with another structure.
  • R ph1 in formula (Ph-1) is independently an alkyl group, an aryl group, a halogen atom, an alkoxy group, a carboxy group, an alkoxycarbonyl group, an acyl group, an acyloxy group, a cyano group, or a sulfonamide group. Is more preferable, and an alkyl group, an aryl group, a halogen atom, or a sulfonamide group is more preferable.
  • R ph2 in formula (Ph-1) is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom, from the viewpoint of development latitude and post-exposure aging developability.
  • N1 in the formula (Ph-1) is preferably 1 or 2, and more preferably 1 from the viewpoint of developability and development latitude.
  • the bonding position of the phenolic hydroxyl group in the formula (Ph-1) is not particularly limited, but from the viewpoint of developability and development latitude, the ortho position (with respect to the bonding position of the nitrogen atom in the formula (Ph-1) ( The o-position) or the para-position (p-position) is preferable, and the para-position is more preferable.
  • N2 in the formula (Ph-1) is preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0.
  • the structural unit having a phenolic hydroxyl group in the side chain preferably has an amide bond from the viewpoint of development latitude and post-exposure aging developability, and is a structural unit represented by the following formula (Ph-2). Is more preferable.
  • R ph1 each independently represent a monovalent substituent
  • R ph2 represents a hydrogen atom, an alkyl group or an aryl group
  • R ph3 represents a hydrogen atom or a methyl group
  • n1 represents an integer of 1 to 4
  • n2 represents an integer of 0 to 4.
  • R ph1, R ph2, n1 and n2 in Formula (Ph-2), have the same meaning as R ph1, R ph2, n1 and n2 in Formula (Ph-1), a preferable embodiment thereof is also the same.
  • R ph3 in formula (Ph-2) is preferably a hydrogen atom.
  • Examples of the monomer forming the structural unit having a phenolic hydroxyl group on the side chain include acrylamide, methacrylamide, acrylic acid ester, methacrylic acid ester having a phenolic hydroxyl group, or hydroxystyrene.
  • the alkali-soluble resin may have one kind of structural unit having a phenolic hydroxyl group in the side chain, or may have two or more kinds.
  • the content of the constituent unit having a phenolic hydroxyl group in the side chain is preferably 10 mol% to 80 mol% with respect to the total amount of the alkali-soluble resin, from the viewpoint of development latitude and post-exposure aging developability. It is more preferably 10 mol% to 60 mol%, particularly preferably 20 mol% to 55 mol%.
  • the molar ratio of the structural unit represented by the formula (1) and the structural unit having a phenolic hydroxyl group in the side chain in the alkali-soluble resin is not particularly limited, but the development latitude and the post-exposure post-exposure developability are not limited. From the viewpoint, it is preferable that the constitutional unit represented by the above formula (1): the constitutional unit having a phenolic hydroxyl group in the side chain is 2: 1 to 1: 2, and 1.5: 1 to 1: 1. It is more preferably 0.5, and particularly preferably 1.2: 1 to 1: 1.2.
  • the alkali-soluble resin preferably further has a structural unit having a cyano group from the viewpoint of development latitude and post-exposure aging developability.
  • the structural unit having a cyano group is preferably a structural unit represented by the following formula (2-1) from the viewpoint of development latitude and post-exposure aging developability, and is represented by the following formula (2-2). It is more preferable that the structural unit is
  • R CN represents a hydrogen atom or a methyl group
  • X CN represents a single bond or — (Y CN ) nCN —Z CN —
  • Y CN represents —CONH— or —COO.
  • Z CN represents an alkylene group, an arylene group, or a group in which at least two groups selected from the group consisting of an alkylene group, an arylene group, and an ether bond are bonded.
  • R CN in formula (2-1) is preferably a hydrogen atom.
  • X CN in formula (2-1) is preferably a single bond.
  • Y CN in formula (2-1) is preferably —CONH—.
  • NCN in the formula (2-1) is preferably 1.
  • the alkylene group for Z CN in formula (2-1) is preferably an alkylene group having 2 to 6 carbon atoms, and more preferably a linear alkylene group having 2 to 6 carbon atoms.
  • the arylene group in Z CN of the formula (2-1) is preferably a phenylene group or a naphthylene group, more preferably a phenylene group.
  • Z CN in the formula (2-1) is preferably an alkylene group, an arylene group or an arylene group-O-alkylene group, and more preferably an alkylene group or an arylene group.
  • Specific examples of the monomer forming the constitutional unit having a cyano group include acrylonitrile, methacrylonitrile, 2-cyanoethyl acrylate, 2-cyanoethyl methacrylate, 2-cyanoethyl acrylamide, 2-cyanoethyl methacrylamide, p-cyanophenyl methacrylamide.
  • acrylonitrile, acrylamide compounds, or methacrylamide compounds are preferable because they have good chemical resistance. Further, among them, acrylonitrile, N-phenylacrylamide compound or N-phenylmethacrylamide compound is particularly preferable.
  • the alkali-soluble resin may have one type of structural unit having a cyano group, or may have two or more types.
  • the content of the structural unit having a cyano group is 1 with respect to the total amount of the alkali-soluble resin from the viewpoint of development latitude and post-exposure developability. It is preferably from 50 mol% to 50 mol%, more preferably from 5 mol% to 40 mol%, and particularly preferably from 10 mol% to 30 mol%.
  • the alkali-soluble resin preferably further has a structural unit having a carboxy group.
  • the structural unit having a carboxy group is preferably a structural unit represented by the following formula (Ac), from the viewpoints of developability, development latitude and post-exposure aging developability.
  • R Ac represents a hydrogen atom or a methyl group.
  • R Ac in formula (Ac) is preferably a hydrogen atom.
  • Specific examples of the monomer forming the constitutional unit having a carboxy group include acrylic acid, methacrylic acid, maleic anhydride, itaconic acid, etc. Examples thereof include carboxylic acids. Among them, acrylic acid or methacrylic acid is preferable, and acrylic acid is more preferable.
  • the alkali-soluble resin may have one kind of the structural unit having a carboxy group, or may have two or more kinds.
  • the content of the structural unit having a carboxy group is 1 with respect to the total amount of the alkali-soluble resin from the viewpoint of development latitude and post-exposure aging developability. It is preferably from 50 to 50 mol%, more preferably from 2 to 40 mol%, and particularly preferably from 5 to 30 mol%.
  • the alkali-soluble resin may have other constitutional units other than those mentioned above.
  • the other structural unit is not particularly limited, but it is preferable to include a structural unit derived from an alkyl (meth) acrylate compound (a structural unit obtained by copolymerizing an alkyl (meth) acrylate compound).
  • Specific examples of the monomer forming the above-mentioned other structural units are preferably the following monomers (m1) to (m9).
  • (M1) Acrylic acid esters and methacrylic acid esters having an aliphatic hydroxyl group such as 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate.
  • (M2) Alkyl acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, benzyl acrylate, 2-chloroethyl acrylate and glycidyl acrylate.
  • Alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, 2-chloroethyl methacrylate, glycidyl methacrylate and the like.
  • (M4) acrylamide, methacrylamide, N-methylolacrylamide, N-ethylacrylamide, N-hexylmethacrylamide, N-cyclohexylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-nitrophenylacrylamide, N-ethyl- Acrylamide or methacrylamide such as N-phenylacrylamide, N-vinylpyrrolidone.
  • (M5) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether and phenyl vinyl ether.
  • (M6) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate.
  • Styrenes such as styrene, ⁇ -methylstyrene, methylstyrene and chloromethylstyrene.
  • (M8) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.
  • Olefins such as ethylene, propylene, isobutylene, butadiene and isoprene.
  • the alkali-soluble resin may have one of the above-mentioned other structural units alone, or may have two or more thereof.
  • the content of the other structural unit is 1 mol% to 50 with respect to the total amount of the alkali-soluble resin, from the viewpoint of development latitude and post-exposure aging developability.
  • the amount is preferably mol%, more preferably 2 mol% to 40 mol%, particularly preferably 5 mol% to 30 mol%.
  • the alkali-soluble resin preferably has a weight average molecular weight (Mw) of 2,000 or more and a number average molecular weight of 500 or more, a weight average molecular weight of 5,000 to 300,000, and a number average molecular weight of 800 to More preferably, it is 250,000.
  • Mw weight average molecular weight
  • the degree of dispersion (weight average molecular weight / number average molecular weight) of the alkali-soluble resin is preferably 1.1 to 10.
  • the above alkali-soluble resins may be used alone or in combination of two or more.
  • the content of the alkali-soluble resin is preferably 1% by mass to 90% by mass, more preferably 3% by mass to 70% by mass, and more preferably 5% by mass. It is particularly preferably from about 50% by mass.
  • the lower layer contains at least the alkali-soluble resin.
  • the content of the alkali-soluble resin in the lower layer is preferably 3% by mass or more, more preferably 10% by mass or more, and further preferably 25% by mass or more, based on the total mass of the lower layer. .
  • the image forming layer contains an infrared absorber.
  • the infrared absorbent is not particularly limited as long as it is a pigment or dye that absorbs infrared light and generates heat, and various pigments or dyes known as infrared absorbents can be used.
  • the pigment commercially available pigments, color index (CI) handbook, "latest pigment handbook” (edited by Japan Pigment Technology Association, 1977), “latest pigment application technology” (CMC Publishing, 1986), and The pigments described in “Printing Ink Technology", CMC Publishing Co., Ltd., 1984) can be used.
  • pigments examples include black pigments, yellow pigments, orange pigments, brown pigments, red pigments, purple pigments, blue pigments, green pigments, fluorescent pigments, metal powder pigments, and polymer-bonded dyes.
  • a quinophthalone pigment, a dyed lake pigment, an azine pigment, a nitroso pigment, a nitro pigment, a natural pigment, a fluorescent pigment, an inorganic pigment, and carbon black can be used.
  • the pigment may be used without surface treatment or may be subjected to conventionally known surface treatment before use.
  • the particle size of the pigment is preferably 0.01 ⁇ m to 10 ⁇ m, more preferably 0.05 ⁇ m to 1 ⁇ m, and further preferably 0.1 ⁇ m to 1 ⁇ m. The above range is preferable from the viewpoint of stability of the pigment dispersion in the coating liquid for forming the image recording layer, uniformity of the image recording layer, and the like.
  • a method for dispersing the pigment for example, a known dispersion technique used in ink production or toner production described in "Latest Pigment Application Technology" (CMC Publishing, 1986) can be used.
  • dyes are preferably mentioned.
  • the infrared absorber that can be used in the present disclosure, commercially available dyes and known ones described in a literature (for example, “Handbook of Dyes” edited by The Society of Synthetic Organic Chemistry, published in 1970) can be used. Specific examples thereof include azo dyes, metal complex salt azo dyes, pyrazolone azo dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, cyanine dyes, and oxonol dyes.
  • these dyes those that absorb at least infrared light or near infrared light are preferable in that they are suitable for use in a laser that emits infrared light or near infrared light, and cyanine dyes are particularly preferable. preferable.
  • Examples of such dyes that absorb at least infrared light or near infrared light include, for example, JP-A-58-125246, JP-A-59-84356, JP-A-59-202829, and JP-A-60-.
  • Cyanine dyes described in JP-A-78787 and the like methine dyes described in JP-A-58-173696, JP-A-58-181690 and JP-A-58-194595, and JP-A-58-112793, JP-A-58-224793, JP-A-59-48187, JP-A-59-73996, JP-A-60-52940, JP-A-60-63744 and the like.
  • cyanine dyes particularly preferred among these dyes are cyanine dyes, phthalocyanine dyes, oxonol dyes, squarylium dyes, pyrylium salts, thiopyrylium dyes, and nickel thiolate complexes.
  • the cyanine dye represented by the following formula (a) is most preferable because it has excellent stability and economy when used in the upper layer of the present disclosure.
  • X 1 represents a hydrogen atom, a halogen atom, a diarylamino group (-NPh 2 ), X 2 -L 1 or a group shown below, X 2 represents an oxygen atom or a sulfur atom, L 1 represents a hydrocarbon group having 1 to 12 carbon atoms, an aromatic ring having a hetero atom, or a hydrocarbon group having 1 to 12 carbon atoms containing a hetero atom.
  • a hetero atom here represents N, S, O, a halogen atom, and Se.
  • Xa ⁇ is defined in the same manner as Za ⁇ described later, and R a is a substituent selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, a substituted or unsubstituted amino group, and a halogen atom. Represents a group.
  • R 21 and R 22 each independently represent a hydrocarbon group having 1 to 12 carbon atoms. From the viewpoint of storage stability of the coating liquid for the image recording layer, R 21 and R 22 are preferably a hydrocarbon group having 2 or more carbon atoms, and further, R 21 and R 22 are bonded to each other to form a 5-membered ring or It is particularly preferable to form a 6-membered ring.
  • Ar 1 and Ar 2 may be the same or different and each represents an aromatic hydrocarbon group which may have a substituent.
  • Preferred aromatic hydrocarbon groups include a benzene ring and a naphthalene ring.
  • Examples of preferable substituents include a hydrocarbon group having 12 or less carbon atoms, a halogen atom, and an alkoxy group having 12 or less carbon atoms.
  • Preferred substituents include an alkoxy group having 12 or less carbon atoms, a carboxy group, or a sulfo group.
  • Za ⁇ represents a counter anion. However, when the cyanine dye represented by the formula (a) has an anionic substituent in its structure and charge neutralization is unnecessary, Za ⁇ is not necessary.
  • Preferred Za ⁇ is a halide ion, a perchlorate ion, a tetrafluoroborate ion, a hexafluorophosphate ion, and a sulfonate ion in view of the storage stability of the coating solution for the image recording layer, and a perchlorate ion is particularly preferred.
  • a perchlorate ion is particularly preferred.
  • Hexafluorophosphate ion, and arylsulfonate ion is particularly preferred.
  • cyanine dye represented by the formula (a) which can be preferably used include, for example, paragraphs 0017 to 0019 of JP 2001-133969 A, paragraphs 0012 to 0038 of JP 2002-40638 A, and JP 2002 A. Examples thereof include those described in paragraphs 0012 to 0023 of JP-A-23360.
  • the cyanine dye A shown below is particularly preferable as the infrared absorber.
  • the infrared absorbers may be used alone or in combination of two or more.
  • the content of the infrared absorbing agent in the image forming layer is 0.01% by mass to 50% by mass based on the total mass of the image forming layer from the viewpoint of sensitivity, uniformity of the image forming layer, and durability. It is preferable that the amount is 0.1% by mass to 30% by mass, more preferably 1.0% by mass to 30% by mass.
  • the image recording layer contains a sulfonium salt compound represented by the following formula (S).
  • R 1 to R 3 each independently represents an alkyl group having 20 or less carbon atoms or an aryl group having 20 or less carbon atoms
  • X ⁇ is a sulfonate ion, a carboxylate ion, or a halogen atom.
  • R 1 to R 3 in formula (S) are each independently an alkyl group having 20 or less carbon atoms or an aryl group having 20 or less carbon atoms and do not bond to each other to form a ring.
  • the alkyl group and aryl group in R 1 to R 3 of the formula (S) may have a substituent.
  • Preferred substituents include a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, or an aryloxy group having 12 or less carbon atoms.
  • R 1 to R 3 in formula (S) are each independently an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms from the viewpoint of development latitude and post-exposure developability.
  • the aryl group having 6 or more and 20 or less carbon atoms is more preferable.
  • the alkyl group may be linear, branched, or have a ring structure, and is preferably an alkyl group having 1 to 8 carbon atoms.
  • the aryl group is preferably an aryl group having one or more halogen atoms, more preferably a phenyl group having one or more halogen atoms, from the viewpoint of development latitude and post-exposure aging developability.
  • a phenyl group having one or more chlorine atoms (chloro group) is particularly preferable.
  • the position having a halogen atom in the phenyl group is preferably at least one position selected from the group consisting of ortho and para positions, and more preferably at least in the para position.
  • the sulfonium salt compound represented by the formula (S) is preferably a triarylsulfonium salt compound from the viewpoint of development latitude and developability after exposure, and the aromatic ring of the aryl group bonded to the sulfur atom is halogen.
  • a triarylsulfonium salt compound having one or more atoms as a whole compound is more preferable, and a triarylsulfonium salt compound having an aromatic ring of each of the three aryl groups bonded to a sulfur atom has one or more halogen atoms respectively. It is more preferable that the aromatic ring of each of the three aryl groups bonded to the sulfur atom is a triarylsulfonium salt compound having one or more chlorine atoms.
  • At least one aromatic ring in the above triarylsulfonium salt compound is a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, from the viewpoint of development latitude and developability after exposure. It is preferable to have at least one group selected from the group consisting of a group and an aryloxy group having 12 or less carbon atoms.
  • X ⁇ in the formula (S) is preferably a sulfonate ion, an inorganic acid ion having a halogen atom or a halide ion, and more preferably a sulfonate ion, from the viewpoint of development latitude and post-exposure aging developability.
  • X ⁇ in the formula (S) preferably has an aromatic group from the viewpoint of development latitude and post-exposure aging developability.
  • X ⁇ in the formula (S) preferably has a phenolic hydroxyl group from the viewpoint of development latitude and post-exposure aging developability.
  • X ⁇ in the formula (S) preferably has a diaryl ketone structure from the viewpoint of development latitude and post-exposure aging developability.
  • X ⁇ in the formula (S) particularly preferably has a phenolic hydroxyl group and a diarylketone structure from the viewpoint of development latitude and post-exposure aging developability.
  • the pKa (acid dissociation constant) of the conjugated acid (XH) of X ⁇ in the formula (S) is preferably less than 5, more preferably ⁇ 10 or more and less than 5, and is ⁇ 10 or more and 2 or less. It is particularly preferable that Note that the pKa in the present disclosure is the pKa in water, and is calculated using ACD / Labs software Ver 8.0 for Microsoft windows ACD / pKa DB ver 8.07 manufactured by Advanced Chemistry Development.
  • X ⁇ in the formula (S) include chloride ion, bromide ion, iodide ion, BF 4 ⁇ , PF 6 ⁇ , trifluoromethanesulfonate ion, p-toluenesulfonate ion, methanesulfonate ion, Alternatively, an anion represented by the following formula (X-1) is preferable, and an anion represented by the following formula (X-1) is particularly preferable.
  • the anion represented by the following formula (X-1) is an anion having a phenolic hydroxyl group and a diarylketone structure.
  • the sulfonium salt compound represented by the above formula (S) is preferably a compound having a maximum absorption wavelength of 400 nm or less from the viewpoint of the handleability of the lithographic printing plate precursor under white light. More preferably, it is a compound having a wavelength of 360 nm or less.
  • Preferred examples of the sulfonium salt compound represented by the above formula (S) include those shown below.
  • the sulfonium salt compounds represented by the above formula (S) may be used alone or in combination of two or more.
  • the content of the sulfonium salt compound represented by the above formula (S) is preferably 0.1% by mass to 50% by mass based on the total mass of the image recording layer from the viewpoint of development latitude and developability after exposure. , 0.5% by mass to 40% by mass is more preferable, and 1% by mass to 30% by mass is particularly preferable.
  • the image recording layer may further contain a resin other than the alkali-soluble resin.
  • the other resin used in the present disclosure is not particularly limited as long as it is a conventionally known resin, and a known alkali-soluble resin can be preferably used. Further, as the other resin, the phenol resins shown below are preferably used.
  • the other resin used in the present disclosure is preferably a phenol resin having a weight average molecular weight of more than 2,000.
  • the phenol resin having a weight average molecular weight of more than 2,000 is a phenol resin containing phenol or a substituted phenol as a structural unit, preferably a novolac resin.
  • the novolak resin is preferably used for the image recording layer in the present disclosure, in the lithographic printing plate precursor, since it causes a strong hydrogen bonding property in the unexposed area and a part of the hydrogen bonding is easily released in the exposed area. It is an alkali-soluble resin.
  • the novolac resin is not particularly limited as long as it contains phenols as a structural unit in the molecule.
  • the novolac resin in the present disclosure is a resin obtained by a condensation reaction of phenol, a substituted phenol shown below, and an aldehyde.
  • the phenol include phenol, isopropylphenol, t-butylphenol, Examples thereof include t-amylphenol, hexylphenol, cyclohexylphenol, 3-methyl-4-chloro-6-t-butylphenol, isopropylcresol, t-butylcresol and t-amylcresol.
  • Preferred are t-butylphenol and t-butylcresol.
  • aldehydes include aliphatic and aromatic aldehydes such as formaldehyde, acetaldehyde, acrolein, and crotonaldehyde. Formaldehyde and acetaldehyde are preferable.
  • examples of the novolac resin in the present disclosure include a condensation polymer of phenol and formaldehyde (phenol formaldehyde resin), a condensation polymer of m-cresol and formaldehyde (m-cresol formaldehyde resin), p -Polycondensation polymer of cresol and formaldehyde (p-cresol formaldehyde resin), polycondensation polymer of m- / p-mixed cresol and formaldehyde (m- / p-mixed cresol-formaldehyde resin), phenol and cresol (m-, Condensation polymer of p- or m- / p-mixture) and formaldehyde (phenol / cresol (m-, p-, or m- / p-mixture) mixed formaldehyde resin), etc.
  • phenol formaldehyde resin phenol formaldehyde resin
  • m-cresol formaldehyde resin a condensation poly
  • novolac resin as described in US Pat. No. 4,123,279, an alkyl group having 3 to 8 carbon atoms such as t-butylphenolformaldehyde resin and octylphenolformaldehyde resin is further used. Examples thereof include a condensation polymer of phenol and formaldehyde having a substituent. Among these novolac resins, phenol formaldehyde resin and phenol / cresol mixed formaldehyde resin are particularly preferable.
  • the weight average molecular weight of the phenol resin is preferably more than 2,000 and 50,000 or less, more preferably 2,500 to 20,000, and particularly preferably 3,000 to 10,000. .
  • the dispersity is preferably 1.1 to 10.
  • the number average molecular weight is a polystyrene equivalent number average molecular weight measured by gel permeation chromatography (GPC) when tetrahydrofuran (THF) is used as a solvent.
  • GPC gel permeation chromatography
  • THF tetrahydrofuran
  • the content of the other resin in the image recording layer in the present disclosure is, from the viewpoint of burning suitability and image forming property, 100 parts by mass of the total content of the resin having an acid group of pKa5 or less and the specific polymer compound.
  • the amount is preferably 90 parts by mass or less, more preferably 50 parts by mass or less, and particularly preferably 30 parts by mass or less.
  • the burning treatment means a high-temperature heat treatment performed after exposure and development of the lithographic printing plate precursor, and the excellent burning suitability means excellent printing durability after the burning treatment.
  • the image forming layer may contain other components, if desired. As other components, known additives can be used. Hereinafter, the acid generator, the acid multiplying agent, and other additives which are optional components in the image forming layer will be described.
  • the image recording layer preferably contains an acid generator.
  • the acid generator is a compound that generates an acid by light or heat, and refers to a compound that decomposes to generate an acid when irradiated with infrared rays or heated at 100 ° C. or higher.
  • the generated acid is preferably a strong acid having a pKa of 2 or less such as sulfonic acid and hydrochloric acid.
  • the acid generated from the acid generator enhances the permeability of the developing solution into the image recording layer in the exposed area of the lithographic printing plate precursor, and further improves the solubility of the image recording layer in the aqueous alkaline solution.
  • the acid generator preferably used in the image recording layer include the acid generators described in paragraphs 0116 to 0130 of WO2016 / 047392.
  • the onium salt compound will be described below.
  • Examples of onium salt compounds that can be suitably used in the present disclosure include compounds known as compounds that generate an acid by being exposed to infrared rays and decomposed by thermal energy generated from the infrared absorber upon exposure.
  • onium salt compounds suitable for the present disclosure include known thermal polymerization initiators and compounds having an onium salt structure described below having a bond with a small bond dissociation energy from the viewpoint of sensitivity.
  • onium salt compounds suitably used in the present disclosure include known diazonium salts, iodonium salts, sulfonium salts other than the sulfonium salt compounds represented by the formula (S), ammonium salts, pyridinium salts, azinium salts, and the like. Of these, diaryliodonium sulfonates, carboxylates, BF 4 ⁇ , PF 6 ⁇ , ClO 4 ⁇ and the like are preferable.
  • Examples of the onium salt compound that can be used as the acid generator in the present disclosure include compounds represented by the following formula (III) or formula (IV).
  • Ar 11 and Ar 12 each independently represent an aryl group having 20 or less carbon atoms, which may have a substituent.
  • a preferable substituent is a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, or an aryloxy group having 12 or less carbon atoms. Is mentioned.
  • Z 11- is a pair selected from the group consisting of halide ion, perchlorate ion, tetrafluoroborate ion, hexafluorophosphate ion, sulfonate ion, and sulfonate ion having a fluorine atom such as perfluoroalkylsulfonate ion. It represents an ion, and is preferably a perchlorate ion, a hexafluorophosphate ion, an aryl sulfonate ion, and a perfluoroalkyl sulfonic acid.
  • Ar 21 represents an optionally substituted aryl group having 1 to 20 carbon atoms.
  • Preferred substituents are a halogen atom, a nitro group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, an alkylamino group having 1 to 12 carbon atoms, Examples thereof include a dialkylamino group having 2 to 12 carbon atoms, an arylamino group having 6 to 12 carbon atoms, and a diarylamino group (the carbon numbers of two aryl groups are each independently 6 to 12).
  • Z 21- represents a counter ion having the same meaning as Z 11- .
  • onium salt compound that can be preferably used in the image recording layer are the same as the compounds described in paragraphs 0121 to 0124 of International Publication WO2016 / 047392.
  • the compounds described as examples of the radical polymerization initiator in paragraphs 0036 to 0045 of JP 2008-195018 can be used. It can be suitably used as the acid generator according to the present disclosure.
  • More preferable examples of the acid generator that can be used in the present disclosure include the following compounds (PAG-4) and (PAG-5). Me represents a methyl group.
  • these acid generators When these acid generators are contained in the image recording layer in the present disclosure, these compounds may be used alone or in combination of two or more kinds.
  • the content of the acid generator is preferably 0.01% by mass to 50% by mass, more preferably 0.1% by mass to 40% by mass, and 0.5% by mass with respect to the total mass of the image recording layer. More preferably, it is from about 30% by mass.
  • the content is within the above range, the sensitivity, which is an effect of the addition of the acid generator, is improved, and the generation of the residual film in the non-image area is suppressed.
  • the image recording layer in the present disclosure may contain an acid multiplying agent.
  • the acid multiplying agent in the present disclosure is a compound substituted with a residue of a relatively strong acid, and is a compound which is easily eliminated in the presence of an acid catalyst to newly generate an acid. That is, it decomposes by an acid-catalyzed reaction to generate an acid again.
  • One or more acids are increased in one reaction, and the acid concentration is accelerated as the reaction progresses, so that the sensitivity is dramatically improved.
  • the strength of the generated acid is preferably 3 or less as an acid dissociation constant (pKa), and more preferably 2 or less. When the acid dissociation constant is 3 or less, the elimination reaction by the acid catalyst is likely to occur.
  • Examples of the acid used for such an acid catalyst include dichloroacetic acid, trichloroacetic acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, naphthalenesulfonic acid and phenylsulfonic acid.
  • the usable acid multiplying agent is the same as those described in paragraphs 0133 to 0135 of WO 2016/047392.
  • the content thereof is preferably 0.01% by mass to 20% by mass, and 0.01% by mass to 10% by mass based on the total mass of the image recording layer. Is more preferable, and 0.1% by mass to 5% by mass is further preferable.
  • the content of the acid proliferating agent is in the above range, the effect of adding the acid proliferating agent is sufficiently obtained, the sensitivity is improved, and the reduction of the film strength of the image area is suppressed.
  • the image recording layer in the present disclosure may contain a development accelerator, a surfactant, a printout agent, a colorant, a plasticizer, a wax agent, etc. as other additives.
  • -Development accelerator- An acid anhydride, a phenol, or an organic acid may be added to the image recording layer in the present disclosure for the purpose of improving sensitivity.
  • Cyclic acid anhydrides are preferred as the acid anhydrides, and specific examples of the cyclic acid anhydrides include phthalic anhydride, tetrahydrophthalic anhydride, and hexahydroanhydride described in US Pat. No. 4,115,128.
  • Phthalic acid, 3,6-endooxytetrahydrophthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride, ⁇ -phenylmaleic anhydride, succinic anhydride, pyromellitic anhydride and the like can be used.
  • Acetic anhydride etc. are mentioned as an acyclic acid anhydride.
  • phenols include bisphenol A, 2,2′-bishydroxysulfone, p-nitrophenol, p-ethoxyphenol, 2,4,4′-trihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 4- Examples include hydroxybenzophenone, 4,4 ', 4 "-trihydroxytriphenylmethane, 4,4', 3", 4 "-tetrahydroxy-3,5,3 ', 5'-tetramethyltriphenylmethane. .
  • Organic acids are described in JP-A-60-88942, JP-A-2-96755, and the like.
  • p-toluenesulfonic acid dodecylbenzenesulfonic acid, p-toluenesulfinic acid, Ethyl sulfuric acid, phenylphosphonic acid, phenylphosphinic acid, phenyl phosphate, diphenyl phosphate, benzoic acid, isophthalic acid, adipic acid, p-toluic acid, 3,4-dimethoxybenzoic acid, phthalic acid, terephthalic acid, 4-cyclohexene Examples include -1,2-dicarboxylic acid, erucic acid, lauric acid, n-undecanoic acid, and ascorbic acid.
  • the proportion of the above-mentioned acid anhydride, phenols and organic acids in the total mass of the image recording layer is preferably 0.05% by mass to 20% by mass, more preferably 0.1% by mass to 15% by mass, and 0.1% by mass. 1% by mass to 10% by mass is particularly preferable.
  • JP-A-62-251740 and JP-A-3-208514 The image recording layer in the present disclosure is described in JP-A-62-251740 and JP-A-3-208514 in order to improve the coating property and to broaden the stability of processing under developing conditions.
  • Such nonionic surfactants, amphoteric surfactants as described in JP-A-59-121044 and JP-A-4-13149, JP-A-62-170950, JP-A-11- Fluorine-containing monomer copolymers as described in JP-A-288093 and JP-A-2003-57820 can be added.
  • nonionic surfactant examples include sorbitan tristearate, sorbitan monopalmitate, sorbitan trioleate, stearic acid monoglyceride and polyoxyethylene nonylphenyl ether.
  • amphoteric activator examples include alkyldi (aminoethyl) glycine, alkylpolyaminoethylglycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine and N-tetradecyl-N, N-betaine.
  • the ratio of the surfactant to the total mass of the image recording layer is preferably 0.01% by mass to 15% by mass, more preferably 0.01% by mass to 5% by mass, and 0.05% by mass to 2.0% by mass. % Is more preferable.
  • -Bakeout agent / colorant- A printout agent for obtaining a visible image immediately after heating by exposure and a dye or pigment as an image colorant can be added to the image recording layer.
  • a dye or pigment as an image colorant can be added to the image recording layer.
  • Examples of the print-out agent and the colorant are described in detail in paragraphs 0122 to 0123 of JP 2009-229917 A, and the compounds described therein can be applied to the present disclosure.
  • the print-out agent and the colorant are preferably added in a proportion of 0.01% by mass to 10% by mass, and in a ratio of 0.1% by mass to 3% by mass, based on the total mass of the image recording layer. Is more preferable.
  • plasticizer may be added to the image recording layer in order to impart flexibility to the coating film.
  • plasticizers are preferably added in a proportion of 0.5% by mass to 10% by mass, more preferably 1.0% by mass to 5% by mass, based on the total mass of the image recording layer. preferable.
  • -Wax agent- A compound that reduces the coefficient of static friction of the surface may be added to the image recording layer for the purpose of imparting resistance to scratches.
  • Examples thereof include compounds having an ester of a long-chain alkylcarboxylic acid.
  • the amount of the wax agent added is preferably 0.1% by mass to 10% by mass, more preferably 0.5% by mass to 5% by mass, based on the total mass of the image recording layer.
  • the image recording layer preferably has an upper layer and a lower layer, and an image recording layer in which the lower layer and the upper layer are arranged in this order on a support (hereinafter, also referred to as a “lithographic printing plate precursor having a two-layer structure”). Is more preferable.
  • the lower layer and the upper layer are preferably formed by separating the two layers.
  • a method of forming the two layers separately for example, a method of utilizing a difference in solvent solubility between a component contained in the lower layer and a component contained in the upper layer, or a method of applying a solvent rapidly after coating the upper layer Examples of the method include drying and removing.
  • the alkali-soluble resin having the constitutional unit represented by the formula (1) and the constitutional unit having a phenolic hydroxyl group in the side chain, the infrared absorber, and the sulfonium salt compound represented by the formula (S) are used in the lower layer or It may be contained in any of the upper layers, but from the viewpoint of printing durability and scratch resistance, the upper layer contains at least an infrared absorbing agent, and the sulfonium salt compound represented by the formula (S), and,
  • the lower layer preferably contains at least an alkali-soluble resin having a structural unit represented by the above formula (1) and a structural unit having a phenolic hydroxyl group in a side chain.
  • a solvent system in which none of the components contained in the lower layer is insoluble is used when the coating liquid for the upper layer is applied. It is a thing. As a result, even if two-layer coating is performed, each layer can be clearly separated to form a coating film.
  • a component insoluble in a solvent such as methyl ethyl ketone or 1-methoxy-2-propanol which dissolves the alkali soluble resin as the upper layer component is selected, and the lower layer is coated using a solvent system which dissolves the lower layer component.
  • the upper layer mainly composed of the alkali-soluble resin is dissolved with methyl ethyl ketone, 1-methoxy-2-propanol or the like, and the resulting layer is coated and dried to form a double layer.
  • high-pressure air is blown from a slit nozzle installed almost at right angles to the running direction of the web, or heating with steam or the like.
  • This can be achieved by applying heat energy as conduction heat from the lower surface of the web from a roll (heating roll) that is internally supplied with the medium, or by combining them.
  • the coating amount of the lower layer component coated on the support of the lithographic printing plate precursor according to the present disclosure after drying is preferably in the range of 0.5 g / m 2 to 4.0 g / m 2 , and is 0.6 g. / M 2 to 2.5 g / m 2 is more preferable. When it is 0.5 g / m 2 or more, printing durability is excellent, and when it is 4.0 g / m 2 or less, image reproducibility and sensitivity are excellent.
  • the coating amount after drying of the upper layer component is preferably in the range of 0.05g / m 2 ⁇ 1.0g / m 2, in the range of 0.08g / m 2 ⁇ 0.7g / m 2 Is more preferable.
  • the combined coating amount of the lower layer and the upper layer after drying is preferably in the range of 0.6 g / m 2 to 4.0 g / m 2 , and in the range of 0.7 g / m 2 to 2.5 g / m 2 . Is more preferable.
  • 0.6 g / m 2 or more printing durability is excellent, and when it is 4.0 g / m 2 or less, image reproducibility and sensitivity are excellent.
  • the support used in the lithographic printing plate precursor according to the present disclosure is not particularly limited as long as it is a dimensionally stable plate-like material having necessary strength and durability, and for example, paper, plastic (for example, , Polyethylene, polypropylene, polystyrene, etc.) laminated paper, metal plate (eg, aluminum, zinc, copper, etc.), plastic film (eg, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate) , Cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.), a paper laminated with or vapor-deposited with the above metals, or a plastic film.
  • plastic for example, Polyethylene, polypropylene, polystyrene, etc.
  • metal plate eg, aluminum, zinc, copper, etc.
  • plastic film eg, cellulose diacetate,
  • a polyester film or an aluminum plate is preferable, and among them, an aluminum plate which has good dimensional stability and is relatively inexpensive is particularly preferable.
  • a suitable aluminum plate is a pure aluminum plate or an alloy plate containing aluminum as a main component and containing a trace amount of a foreign element, and may be a plastic film on which aluminum is laminated or vapor-deposited.
  • the foreign elements contained in the aluminum alloy include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel and titanium.
  • the content of the foreign element in the alloy is preferably 10 mass% or less.
  • Aluminum which is particularly suitable in the present disclosure is pure aluminum, but completely pure aluminum is difficult to produce due to refining technology, and thus may contain slightly different elements.
  • the composition of the aluminum plate applied to the present disclosure is not specified, and an aluminum plate of a publicly known and publicly known material can be appropriately used.
  • the aluminum plate used in the present disclosure preferably has a thickness of 0.1 mm to 0.6 mm, more preferably 0.15 mm to 0.4 mm, and particularly preferably 0.2 mm to 0.3 mm. preferable.
  • Such aluminum plate may be subjected to surface treatment such as surface roughening treatment and anodizing treatment, if necessary.
  • surface treatment such as surface roughening treatment and anodizing treatment
  • a degreasing treatment with a surfactant, an organic solvent or an alkaline aqueous solution, a rough surface as described in paragraphs 0167 to 0169 of JP2009-175195A Chemical treatment, anodization treatment, etc. are appropriately performed.
  • the aluminum surface that has been subjected to the anodizing treatment is optionally subjected to a hydrophilic treatment.
  • hydrophilic treatment examples include an alkali metal silicate (for example, sodium silicate aqueous solution) method, a treatment with potassium fluorozirconate, or polyvinylphosphonic acid as disclosed in paragraph 0169 of 2009-175195. Used. Further, the support described in JP 2011-245844 A is also preferably used.
  • an undercoat layer can be provided between the support and the image forming layer, if necessary.
  • various organic compounds are used, for example, carboxymethyl cellulose, phosphonic acids having an amino group such as dextrin, organic phosphonic acid, organic phosphoric acid, organic phosphinic acid, amino acids, and a hydroxy group.
  • Preferable examples are the hydrochlorides of the amines that it has.
  • These undercoat layer components may be used alone or in combination of two or more.
  • the coating amount of the undercoat layer is preferably 2 mg / m 2 to 200 mg / m 2 , and more preferably 5 mg / m 2 to 100 mg / m 2 . When the coating amount is within the above range, sufficient printing durability can be obtained.
  • a back coat layer is preferably provided on the surface of the support opposite to the side on which the image recording layer is provided, if necessary.
  • the back coat layer is composed of an organic polymer compound described in JP-A-5-45885 and a metal oxide obtained by hydrolyzing and polycondensing an organic or inorganic metal compound described in JP-A-6-35174.
  • a coating layer is preferably used.
  • silicon alkoxy compounds such as Si (OCH 3 ) 4 , Si (OC 2 H 5 ) 4 , Si (OC 3 H 7 ) 4 and Si (OC 4 H 9 ) 4 are inexpensively available. It is particularly preferable because the coating layer of the metal oxide obtained therefrom is excellent in the resistance to developing solution.
  • the method for producing a lithographic printing plate according to the present disclosure includes an exposure step of exposing the lithographic printing plate precursor according to the present disclosure in an imagewise manner, and a developing step of developing with a developing solution in this order.
  • the developer is preferably an alkali developer having a pH of 9 or more from the viewpoint of suppressing silicate debris.
  • the method for producing a lithographic printing plate according to the present disclosure from the viewpoint of suppressing silicate residue, a step of imagewise exposing the lithographic printing plate precursor according to the present disclosure using an infrared laser, and does not include a silicate compound. It is preferable to include a step of developing using an alkaline developer having a pH of 9 or more.
  • the method for producing a lithographic printing plate according to the present disclosure includes an exposure step of imagewise exposing the lithographic printing plate precursor according to the present disclosure.
  • a light source of actinic rays used for image exposure of the lithographic printing plate precursor according to the present disclosure a light source having an emission wavelength in the near infrared to infrared region is preferable, and a solid laser and a semiconductor laser are more preferable.
  • the laser output is preferably 100 mW or more, and it is preferable to use a multi-beam laser device in order to shorten the exposure time.
  • the exposure time per pixel is preferably within 20 ⁇ sec.
  • the energy applied to the lithographic printing plate precursor is preferably 10 mJ / cm 2 to 300 mJ / cm 2 . Within the above range, laser ablation can be suppressed and the image can be prevented from being damaged.
  • the exposure in the present disclosure can be performed by overlapping the light beams of the light source.
  • the overlap means that the sub-scanning pitch width is smaller than the beam diameter.
  • the overlap can be quantitatively expressed by FWHM / sub-scanning pitch width (overlap coefficient) when the beam diameter is expressed by the full width at half maximum (FWHM) of the beam intensity. In the present disclosure, this overlap coefficient is preferably 0.1 or more.
  • the light source scanning method of the exposure apparatus that can be used in the present disclosure is not particularly limited, and a cylinder outer surface scanning method, a cylinder inner surface scanning method, a flat surface scanning method, or the like can be used.
  • the light source channel may be a single channel or a multi-channel, but in the case of the cylindrical outer surface system, the multi-channel is preferably used.
  • the method for producing a lithographic printing plate according to the present disclosure includes a developing step of developing with a developing solution.
  • the developer used in the developing step is preferably an alkali developer having a pH of 9 or more, more preferably an alkali developer having a pH of 9 or more and containing no silicate compound.
  • the silicate compound include silicon dioxide.
  • the developer containing no silicate compound is also referred to as a non-silicate developer, and the development using the non-silicate developer is also referred to as a non-silicate development.
  • the non-silicate developer the non-silicate developer described in JP 2001-209172 A is preferably used.
  • the pH of the alkaline developer is preferably 12.5 to 13.5.
  • the alkaline developer preferably contains an organic compound having a buffering action and a basic compound.
  • the organic compound having a buffering action include saccharides (especially those represented by the general formula (I) or (II)) described as a compound having a buffering action in JP-A-8-220775, and oximes (especially General formula (III)), phenols (particularly represented by general formula (IV)), fluorinated alcohols (particularly represented by general formula (V)) and the like.
  • the compounds represented by the general formulas (I) to (V) preferred are the saccharides represented by the general formula (I) or (II) and the phenols represented by the general formula (V).
  • non-reducing sugars such as saccharose or sulfosalicylic acid are more preferable.
  • the above-mentioned non-reducing sugars include trehalose-type oligosaccharides having reducing groups bound to each other, glycosides having reducing groups of saccharides bound to non-saccharides, sugar alcohols hydrogenated to reduce sugars, and the like.
  • Examples of the trehalose-type oligosaccharides include saccharose and trehalose, and examples of the glycosides include alkyl glycosides, phenol glycosides, mustard oil glycosides, and the like.
  • Examples of the sugar alcohol include D, L-arabite, ribit, xylit, D, L-sorbit, D, L-annite, D, L-idit, D, L-talit, Kiricit, and alodulcit.
  • maltitol obtained by hydrogenation of a disaccharide, a reduced form (reduced starch syrup) obtained by hydrogenation of an oligosaccharide, and the like can be preferably mentioned.
  • sugar alcohol and saccharose are preferable as the non-reducing sugar, and among them, D-sorbit, sucrose and reduced starch syrup are more preferable because they have a buffering action in an appropriate pH range.
  • the organic compounds having a buffering effect may be used alone or in combination of two or more.
  • the content of the organic compound having a buffering effect is preferably 0.1% by mass to 30% by mass, more preferably 1% by mass to 20% by mass, based on the total mass of the developer.
  • An alkaline agent as a basic compound can be appropriately selected from the conventionally known compounds and combined with the above-mentioned organic compound having a buffering action.
  • the alkaline agent include sodium hydroxide, potassium hydroxide, lithium hydroxide, trisodium phosphate, tripotassium phosphate, triammonium phosphate, disodium phosphate, dipotassium phosphate, diammonium phosphate, Inorganic alkaline agents such as sodium carbonate, potassium carbonate, ammonium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, ammonium hydrogen carbonate, sodium borate, potassium borate, ammonium borate, potassium citrate, tripotassium citrate, sodium citrate Etc.
  • organic alkali agents such as neuramis, ethyleneimine, ethylenediamine, pyridine and the like.
  • sodium hydroxide or potassium hydroxide is preferable as the basic compound.
  • the reason is that the pH can be adjusted in a wide pH range by adjusting the addition amount to the non-reducing sugar.
  • trisodium phosphate, tripotassium phosphate, sodium carbonate, potassium carbonate and the like are preferable because they have a buffering effect.
  • the above basic compounds may be used alone or in combination of two or more.
  • the content of the basic compound is not particularly limited, and it may be added to the developing solution in an amount that provides a desired pH.
  • the developer preferably contains a surfactant from the viewpoint of processability.
  • the surfactant used in the developer may be any of anionic, nonionic, cationic, and amphoteric surfactants, but as described above, anionic and nonionic surfactants. Agents are preferred.
  • anionic, nonionic, cationic and amphoteric surfactants used in the developing solution in the present disclosure those described in paragraphs 0128 to 0131 of JP2013-134341A can be used.
  • the HLB value of the surfactant is preferably 6 or more, more preferably 8 or more.
  • anionic surfactants and nonionic surfactants are preferable, and anionic surfactants containing sulfonic acid or sulfonate, and nonionics having an aromatic ring and an ethylene oxide chain. Surfactants are especially preferred.
  • the surfactants can be used alone or in combination.
  • the content of the surfactant in the developer is preferably 0.01% by mass to 10% by mass, more preferably 0.01% by mass to 5% by mass.
  • the developer 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 and the like.
  • a wetting agent e.g., a preservative, a chelate compound, a defoaming agent, an organic acid, an organic solvent, an inorganic acid, an inorganic salt and the like.
  • the wetting agent described in paragraph 0141 of JP2013-134341A can be preferably used.
  • the wetting agents may be used alone or in combination of two or more.
  • the wetting agent is preferably used in an amount of 0.1% by mass to 5% by mass, based on the total mass of the developer.
  • the preservative described in paragraph 0142 of JP2013-134341A can be preferably used. It is preferable to use two or more preservatives in combination so as to be effective against various molds and sterilizations.
  • the addition amount of the preservative is an amount that exerts a stable effect on bacteria, molds, yeasts and the like, and varies depending on the types of bacteria, molds, yeasts, but it is 0 for the total mass of the developer. A range of 0.01% by mass to 4% by mass is preferable.
  • the chelate compound described in paragraph 0143 of JP2013-134341A can be preferably used.
  • the chelating agent is selected so that it stably exists in the developer composition and does not impair the printability.
  • the addition amount is preferably 0.001% by mass to 1.0% by mass with respect to the total mass of the developer.
  • the defoaming agent described in paragraph 0144 of JP2013-134341A can be preferably used.
  • the content of the defoaming agent is preferably in the range of 0.001% by mass to 1.0% by mass with respect to the total weight of the developer.
  • the defoaming agent described in paragraph 0145 of JP2013-134341A can be preferably used.
  • the content of the organic acid is preferably 0.01% by mass to 0.5% by mass with respect to the total mass of the developer.
  • organic solvent examples include aliphatic hydrocarbons (hexane, heptane, “Isopar E, H, G” (manufactured by Esso Chemical Co., Ltd.), gasoline, or kerosene), aromatic hydrocarbons (toluene, Xylene) or halogenated hydrocarbons (methylene dichloride, ethylene dichloride, trichlene, monochlorobenzene, etc.) and polar solvents.
  • aliphatic hydrocarbons hexane, heptane, “Isopar E, H, G” (manufactured by Esso Chemical Co., Ltd.)
  • aromatic hydrocarbons toluene, Xylene
  • halogenated hydrocarbons methylene dichloride, ethylene dichloride, trichlene, monochlorobenzene, etc.
  • polar solvents examples include alcohols (methanol, ethanol, propanol, isopropanol, benzyl alcohol, ethylene glycol monomethyl ether, 2-ethoxyethanol, etc.), ketones (methyl ethyl ketone, cyclohexanone, etc.), esters (ethyl acetate, methyl lactate, propylene). Glycol monomethyl ether acetate, etc.) and others (triethyl phosphate, tricresyl phosphate, N-phenylethanolamine, N-phenyldiethanolamine, etc.) and the like.
  • the above organic solvent is insoluble in water, it can be solubilized in water with a surfactant or the like before use.
  • the concentration of the solvent is preferably less than 40 mass% from the viewpoint of safety and flammability.
  • 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% by mass to 0.5% by mass with respect to the total mass of the developer.
  • the developing temperature is not particularly limited as long as it can be developed, but is preferably 60 ° C. or lower, more preferably 15 ° C. to 40 ° C.
  • the developing solution may become fatigued depending on the processing amount, and therefore the replenishing solution or a fresh developing solution may be used to recover the processing ability.
  • a method of performing alkali development, removing the alkali in the post-water washing step, performing gum treatment in the gumming step, and drying in the drying step can be exemplified.
  • a method of simultaneously performing pre-washing, developing and gumming can be preferably exemplified by using an aqueous solution containing carbonate ion, hydrogen carbonate ion and a surfactant. Therefore, the pre-water washing step does not have to be particularly performed, and it is preferable to perform the pre-water washing, the development and the gumming in one bath only after using one solution, and then to perform the drying step. After the development, it is preferable to remove excess developer using a squeeze roller or the like and then perform drying.
  • Development process can be preferably carried out by an automatic processor equipped with a rubbing member.
  • the automatic processor for example, the automatic processor described in JP-A-2-220061 and JP-A-60-59351, which performs rubbing treatment while conveying the planographic printing plate precursor after image exposure, and a cylinder
  • the lithographic printing plate precursor after image exposure set on the above is subjected to rubbing treatment while rotating a cylinder
  • an automatic processor using a rotating brush roll as the rubbing member is particularly preferable.
  • the rotating brush roll used in the present disclosure can be appropriately selected in consideration of the scratch resistance of the image area, the rigidity of the support of the planographic printing plate precursor, and the like.
  • a known roll formed by planting a brush material on a plastic or metal roll can be used.
  • a metal or plastic in which brush materials are implanted in rows as described in JP-A-58-159533 and JP-A-3-100554, and JP-B-62-167253. It is possible to use a brush roll in which the groove-shaped material is wound around a plastic or metal roll serving as a core in a radial pattern without a gap.
  • plastic fibers for example, polyester type such as polyethylene terephthalate and polybutylene terephthalate, polyamide type such as nylon 6.6 and nylon 6.10, polyacryl type such as polyacrylonitrile, alkyl poly (meth) acrylate
  • Polyolefin-based synthetic fibers such as polypropylene and polystyrene
  • fibers having a hair diameter of 20 ⁇ m to 400 ⁇ m and a hair length of 5 mm to 30 mm can be preferably used.
  • the outer diameter of the rotating brush roll is preferably 30 mm to 200 mm, and the peripheral speed of the tip of the brush rubbing the plate surface is preferably 0.1 m / sec to 5 m / sec. It is preferable to use a plurality of rotating brush rolls.
  • the rotating brush roll may be rotated in the same direction or in the opposite direction with respect to the conveying direction of the lithographic printing plate precursor, but when using two or more rotating brush rolls, at least one rotating brush roll is used. It is preferable that the rotating brush rolls of 1 rotate in the same direction and at least one rotating brush roll rotate in the opposite direction. This further ensures removal of the image recording layer in the non-image area. Further, it is also effective to swing the rotating brush roll in the rotation axis direction of the brush roll.
  • the method for producing a lithographic printing plate according to the present disclosure the liquid activity of the alkaline developer is measured by the conductivity of the alkaline developer, and a replenisher is added according to the measured value to obtain the target conductivity. Therefore, it is preferable to include a step of controlling the liquid activity (also referred to as a “control step”).
  • the alkali developing solution in the control step is preferably an alkali developing solution containing no silicate compound and having a pH of 9 or more.
  • the “replenisher” is a processing solution replenished to keep the developing performance constant.
  • the replenishing solution there are those prepared by diluting the replenishing solution undiluted solution with a diluting solution (eg, water), and those using the replenishing solution undiluted solution as it is without diluting it. Is preferably prepared by diluting the replenisher stock solution with a diluent.
  • a replenishing method there is a method of replenishing the developing solution with a replenishing solution prepared by diluting in advance, or a method of directly replenishing the developing solution with the replenishing solution stock solution and the diluting solution separately.
  • an electric conductivity sensor As a method for measuring the electric conductivity of the alkaline developer, it is preferable to use an electric conductivity sensor.
  • the conductivity sensor for measuring the conductivity of the developer a known means such as an AC conductivity meter, an AC bridge meter, or other conductivity meter can be used.
  • the measured current value, oscillation frequency, etc. of the above-mentioned measuring device differ in optimum conditions depending on the composition of the developing solution, etc., but the current value is low to some extent in terms of the apparatus and to prevent electrolysis of the water-soluble developing solution. Is preferable, and several hundred mA to several ⁇ A is preferable.
  • the frequency is preferably several hundreds Hz to several hundreds kHz from the relationship with the electrostatic capacitance component in the developing solution.
  • the value of the conductivity of the developer containing the electrolyte depends on the temperature of the aqueous solution, and decreases as the temperature of the solution rises. Therefore, it is more preferable to measure the electric conductivity with a measuring instrument equipped with a temperature sensor and a temperature compensation circuit. Further, in the control device for controlling replenishment, it is also possible to convert the actually measured liquid resistance value and liquid temperature into an electric conductivity value at a predetermined temperature for temperature compensation.
  • the sensor installation position of the AC conductivity meter, the AC bridge meter, or other conductivity meter may be a place where the AC conductivity value of the developer can be measured by being immersed in the developer at the time of measurement.
  • the preferred position is the developing solution circulation system, especially in the developing tank or the circulation pipe.
  • As the detection unit a known measurement cell using platinum, stainless steel or the like for the electrode can be used.
  • a drying step continuously or discontinuously. Drying is performed with hot air, infrared rays, far infrared rays, or the like.
  • an automatic processor preferably used in the method for producing a lithographic printing plate according to the present disclosure, an apparatus having a developing unit and a drying unit is used, and a lithographic printing plate precursor is developed and gummed in a developing tank. And then dried in the drying section to obtain a lithographic printing plate.
  • the printing plate after development can be heated for the purpose of improving printing durability.
  • the heating temperature is preferably in the range of 200 ° C to 500 ° C.
  • the molecular weight is the weight average molecular weight (Mw) and the ratio of the constitutional units is a mole percentage, except for those specifically specified.
  • Mw weight average molecular weight
  • the weight average molecular weight (Mw) is a value measured as a polystyrene conversion value by a gel permeation chromatography (GPC) method.
  • ⁇ Surface treatment> As the surface treatment, the following various treatments (a) to (k) were continuously performed. After each treatment and washing with water, drainage was performed with a nip roller.
  • FIG. 1 Mechanical surface roughening treatment
  • a device such as shown in FIG. 1 was used to supply a suspension of an abrasive (pumice) having a specific gravity of 1.12 and water as a polishing slurry liquid to the surface of an aluminum plate. Meanwhile, mechanical roughening treatment was performed by a rotating roller-shaped nylon brush.
  • 1 is an aluminum plate
  • 2 and 4 are roller brushes
  • 3 is a polishing slurry liquid
  • 5, 6, 7 and 8 are support rollers.
  • the average particle size of the abrasive was 30 ⁇ m, and the maximum particle size was 100 ⁇ m.
  • the material of the nylon brush was 6.10 nylon, the bristle length was 45 mm, and the bristle diameter was 0.3 mm.
  • the nylon brush was prepared by forming holes in a stainless steel cylinder having a diameter of 300 mm and densely implanting the bristles. Three rotating brushes were used. The distance between the two support rollers ( ⁇ 200 mm) below the brush was 300 mm. The brush roller was pressed until the load of the drive motor for rotating the brush became 7 kW plus with respect to the load before the brush roller was pressed against the aluminum plate. The rotating direction of the brush was the same as the moving direction of the aluminum plate. The rotation number of the brush was 200 rpm (revolutions per minute).
  • Desmutting treatment was carried out by spraying with a 1% by weight nitric acid concentration aqueous solution (containing 0.5% by weight of aluminum ion) at a temperature of 30 ° C., followed by washing with water by spraying.
  • the nitric acid aqueous solution used for the desmutting treatment was the waste liquid of the step of performing the electrochemical surface roughening treatment using an alternating current in the nitric acid aqueous solution.
  • Electrochemical surface roughening treatment was continuously performed using an alternating voltage of 60 Hz. At this time, the electrolytic solution was a 10.5 g / L nitric acid aqueous solution (containing 5 g / L of aluminum ions and 0.007% by mass of ammonium ions), and the liquid temperature was 50 ° C.
  • the AC power supply waveform is the waveform shown in FIG. 2, in which the time TP required for the current value to reach the peak from zero is 0.8 msec, the duty ratio is 1: 1, and a trapezoidal rectangular wave AC is used, with the carbon electrode as the counter electrode.
  • An electrochemical graining treatment was performed. Ferrite was used for the auxiliary anode. The electrolytic cell used was that shown in FIG.
  • the electrolytic cell (radial cell) shown in FIG. 3 includes a main electrolytic cell 40 including a radial drum roller 12 and main electrodes 13a and 13b, an auxiliary anode tank 50 including an auxiliary anode 18, thyristors 19a and 19b, and an AC power supply. 20 and.
  • the electrolytic treatment liquid 14 is supplied to the aluminum plate 11 conveyed to the electrolytic liquid passage 17 via the electrolytic liquid supply ports 15 and 16.
  • the current density was 30 A / dm 2 at the peak value of the current, and the amount of electricity was 220 C / dm 2 as the total amount of electricity when the aluminum plate was the anode. 5% of the current flowing from the power source was shunted to the auxiliary anode. Then, washing with water was performed by spraying.
  • (E) Alkaline etching treatment An aluminum plate is subjected to etching treatment by spraying with an aqueous solution having a caustic soda concentration of 26 mass% and an aluminum ion concentration of 6.5 mass% at 32 ° C to dissolve the aluminum plate at 0.50 g / m 2 . Removes the smut component composed mainly of aluminum hydroxide generated when electrochemical roughening treatment was performed using the alternating current in the previous stage, and melts the edge part of the generated pit to smooth the edge part. did. Then, washing with water was performed by spraying.
  • Desmutting treatment was performed by spraying with a 15% by weight nitric acid aqueous solution (containing 4.5% by weight of aluminum ion) at a temperature of 30 ° C., and then washed with water by spraying.
  • nitric acid aqueous solution used for the desmut a waste liquid from the step of performing an electrochemical graining treatment using an alternating current in the nitric acid aqueous solution was used.
  • Electrochemical surface roughening treatment was continuously performed using an alternating voltage of 60 Hz.
  • the electrolytic solution at this time was a 5.0 g / L hydrochloric acid aqueous solution (containing 5 g / L of aluminum ions), and the temperature was 35 ° C.
  • the AC power supply waveform is the waveform shown in FIG. 2, and the time TP from when the current value reaches zero to the peak is 0.8 msec, the duty ratio is 1: 1, and the trapezoidal rectangular wave AC is used to drive the carbon electrode.
  • Electrochemical roughening treatment was performed as a counter electrode. Ferrite was used for the auxiliary anode.
  • the electrolytic cell used was that shown in FIG.
  • the current density was 25 A / dm 2 at the peak value of the current, and the amount of electricity was 50 C / dm 2 as the total amount of electricity when the aluminum plate was the anode. Then, washing with water was performed by spraying.
  • (H) Alkaline etching treatment An aluminum plate is subjected to etching treatment by spraying at 32 ° C. using an aqueous solution having a caustic soda concentration of 26 mass% and an aluminum ion concentration of 6.5 mass% to dissolve the aluminum plate at 0.10 g / m 2 . Removes the smut component consisting mainly of aluminum hydroxide generated when electrochemical roughening treatment was performed using the alternating current in the previous stage, and melts the edge part of the generated pit to smooth the edge part. did. Then, washing with water was performed by spraying.
  • Desmutting treatment was carried out by spraying with a 25% by mass aqueous solution of sulfuric acid (containing 0.5% by mass of aluminum ion) at a temperature of 60 ° C., followed by washing with water by spraying.
  • the anodizing device currents from the power source 67a and the power source 67b flow to the first power feeding electrode 65a provided in the first power feeding portion 62a, flow to the aluminum plate 11 via the electrolytic solution, and then to the first electrolytic portion 63a. Then, an anodic oxide film is formed on the surface of the aluminum plate 11, passes through the electrolytic electrodes 66a and 66b provided in the first electrolytic portion 63a, and returns to the electrodes 67a and 67b.
  • the amount of electricity supplied from the power sources 67a and 67b to the first power supply unit 62a is equal to the amount of electricity supplied from the power sources 67c and 67d to the second power supply unit 62b, and the first electrolysis unit 63a and the second electrolysis unit 63a
  • the current densities at 63b were both about 30 A / dm 2 .
  • power is fed through the oxide film surface of 1.35 g / m 2 generated in the first electrolytic portion 63a.
  • the final amount of oxide film was 2.7 g / m 2 .
  • (K) Alkali metal silicate treatment By immersing the aluminum support obtained by anodizing treatment in a treatment tank of a 1% by mass aqueous solution of sodium silicate No. 3 at a temperature of 30 ° C for 10 seconds, the alkali metal silicate is treated. Acid salt treatment (silicate treatment) was performed. After that, washing with well water was performed by spraying to obtain a support having a surface silicate hydrophilized. On the aluminum support treated with an alkali metal silicate obtained as described above, an undercoat liquid having the following composition was applied and dried at 80 ° C. for 15 seconds to form a coating film. The coating amount of the coating film after drying was 15 mg / m 2 .
  • Et represents an ethyl group.
  • ⁇ Novolak resin (2,3-xylenol / m-cresol / p-cresol ratio 10/20/70, weight average molecular weight 3,300): 0.192 parts
  • Cyanine dye A (the following compound): 0.134 parts 4,4'-bishydroxyphenyl sulfone: 0.126 parts Tetrahydrophthalic anhydride: 0.190 parts p-Toluenesulfonic acid: 0.008 parts 3-Methoxy-4-diazophenylamine hexafluorophosphate: 0.032 parts-Ethyl violet counter ion changed to 6-hydroxynaphthalenesulfonic acid: 0.0781 parts-Polymer 1 (polymer shown below): 0.035 parts-Methyl ethyl ketone: 25.41 parts-1- Methoxy
  • -Polymer 1 0.015 part-Polymer 2 (polymer shown below): 0.00328 part-Sulfonium salt compound consisting of cation and anion described in Table 1: Addition amount described in Table 1 (for example, Example 1 Will be 0.08 parts.) -Surfactant (Megafac F-780F, manufactured by DIC Corporation: 0.008 parts) -Methyl ethyl ketone: 6.79 parts-1-Methoxy-2-propanol: 13.07 parts
  • the developing solution was prepared by diluting and mixing the developing solutions XP-D and XP-DR manufactured by FUJIFILM Corporation and changing the conductivity between 80 to 100 mS / cm and every 2 mS / cm. .
  • the liquid feeling of the developing solution is low, the development in the exposed area becomes insufficient and a residual film is generated in the non-image area.
  • the liquid feeling of the developing solution is high, the surface of the unexposed portion is developed and the film thickness is reduced, so that a good image cannot be obtained.
  • the width of the electric conductivity of the developer in which neither the residual film in the non-image area nor the film loss in the image area was generated was evaluated for each lithographic printing plate precursor as an index of the development latitude.
  • the lithographic printing plate precursor thus obtained was imagewise written with a test pattern using a Trendsetter manufactured by Creo at a beam intensity of 9 W and a drum rotation speed of 150 rpm. After that, using a Fuji Film PS developer LP-940H (diluted to have an electric conductivity of 43 mS / cm) PS processor LP940H, a development temperature of 30 ° C. and a development time of 12 The development was performed for 20 seconds to 20 seconds. At this time, the developing time was set to the time at which the non-image areas of each level were completely dissolved and the respective images could be formed.
  • the lithographic printing plate precursor thus obtained was image-wise written with a test pattern by a Trendsetter manufactured by Creo at a beam intensity of 9 W and a drum rotation speed of 150 rpm.
  • the exposed lithographic printing plate precursor was allowed to stand in an environment of a temperature of 25 ° C. and a humidity of 70% RH for 30 minutes.
  • a Fuji Film PS developer LP-940H diluted to have an electric conductivity of 43 mS / cm
  • a development temperature of 30 ° C. and a development time of 12 Development was carried out in seconds to 30 seconds. At this time, the developing time was set to the time at which the non-image areas of each level were completely dissolved and the respective images could be formed.
  • -Development residue (silicate residue) inhibition evaluation The obtained lithographic printing plate precursor was entirely exposed by a Trendsetter manufactured by Creo at a beam intensity of 9 W and a drum rotation speed of 150 rpm. The exposed plate was evaluated for development residue (silicate residue) according to the following procedures (1) to (3).
  • the developing solution in which the exposure plate was dissolved was transferred to a resin container and left standing overnight.
  • the state of dregs of the stationary developer was visually evaluated according to the following evaluation criteria. 5: No debris during development in (1) above. One day and night, leave it at rest without any residue.
  • the structural unit a in Table 1 represents a structural unit represented by the above formula (1), and the structural unit b represents a structural unit having a phenolic hydroxyl group in the side chain. Further, the composition ratio (mol ratio) of the alkali-soluble resin shown in Table 1 is described in order from the constitutional unit shown on the left of Table 1. For example, in Example 7, a-1 is 28 mol%. , B-1 is 26 mol%, c-1 is 20 mol%, c-4 is 6 mol%, and c-5 is 20 mol%. Further, details of each abbreviation shown in Table 1 are shown below. a-1 to a-3: structural units shown below
  • Cyanine dye B the following compound
  • An-1 to an-7 the following anions
  • Example 24 On the support obtained in the same manner as in Example 1, a single layer coating solution having the following composition was applied so that the coating amount was 1.2 g / m 2, and dried to form a recording layer. I got the original planographic printing plate.
  • ⁇ Single layer coating liquid> -Alkali-soluble resin described in Example 1: 2.625 parts-m, p-cresol novolac resin (m / p ratio 6/4, weight average molecular weight 4,500, containing 0.8% by mass of unreacted cresol) : 0.525 part Cyanine dye A: 0.15 part 4,4'-bishydroxyphenyl sulfone: 0.225 part Tetrahydrophthalic anhydride: 0.3 part p-Toluenesulfonic acid: 0.015 part ⁇ 3-Methoxy-4-diazophenylamine hexafluorophosphate: 0.045 part ⁇ Ethyl violet counter ion changed to 6-hydroxynaphthalenesulfonic acid: 0.1125 part ⁇ Surfactant (MegaFac F-780F , DIC Co., Ltd .: 0.0525 parts, methyl ethyl ketone: 22.5 parts, 1-methoxy-2-propanol: 11.25 parts,
  • the lithographic printing plate precursors of Examples 1 to 24, which are the lithographic printing plate precursors according to the present disclosure were compared with the lithographic printing plate precursors of Comparative Examples 1 to 3 after the exposure. Excellent developability. Further, it can be seen that the lithographic printing plate precursors of Examples 1 to 24, which are lithographic printing plate precursors according to the present disclosure, can provide lithographic printing plates excellent in development latitude.

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  • Materials For Photolithography (AREA)

Abstract

La présente invention concerne : un précurseur de plaque d'impression planographique qui a une couche d'enregistrement d'image sur un corps de support, la couche d'enregistrement d'image contenant un absorbeur d'infrarouges, un composé de sel de sulfonium représenté par la formule (S), et une résine soluble dans les alcalis ayant un motif constitutif représenté par la formule (1) et un motif constitutif ayant un groupe hydroxyle phénolique sur une chaîne latérale ; et un procédé de production d'une plaque d'impression planographique qui utilise le précurseur de plaque d'impression planographique susmentionné. Dans la formule (1), R représente un groupe alkyle ou un groupe aryle. Dans la formule (S), R1 à R3 représentent chacun indépendamment un groupe alkyle ne comportant pas plus de 20 atomes de carbone ou un groupe aryle ne comportant pas plus de 20 atomes de carbone, et X- représente un ion sulfonate, un ion carboxylate, un ion acide inorganique ayant un atome d'halogène, ou un ion halogénure.
PCT/JP2019/038262 2018-10-17 2019-09-27 Précurseur de plaque d'impression planographique et procédé de production de plaque d'impression planographique WO2020080067A1 (fr)

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JP2018-196147 2018-10-17

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH075684A (ja) * 1991-07-02 1995-01-10 Okamoto Kagaku Kogyo Kk アルカリ現像型感光性組成物
JP2007025354A (ja) * 2005-07-19 2007-02-01 Fujifilm Holdings Corp 画像形成材料
JP2007321104A (ja) * 2006-06-02 2007-12-13 Okamoto Kagaku Kogyo Kk 平版印刷版用原版
JP2008233496A (ja) * 2007-03-20 2008-10-02 Fujifilm Corp 感光性平版印刷版原版
JP2009294352A (ja) * 2008-06-04 2009-12-17 Konica Minolta Medical & Graphic Inc 印刷版材料用樹脂組成物および平版印刷版材料
CN103879169A (zh) * 2012-12-24 2014-06-25 乐凯华光印刷科技有限公司 一种耐uv油墨的阳图热敏ctp版材

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH075684A (ja) * 1991-07-02 1995-01-10 Okamoto Kagaku Kogyo Kk アルカリ現像型感光性組成物
JP2007025354A (ja) * 2005-07-19 2007-02-01 Fujifilm Holdings Corp 画像形成材料
JP2007321104A (ja) * 2006-06-02 2007-12-13 Okamoto Kagaku Kogyo Kk 平版印刷版用原版
JP2008233496A (ja) * 2007-03-20 2008-10-02 Fujifilm Corp 感光性平版印刷版原版
JP2009294352A (ja) * 2008-06-04 2009-12-17 Konica Minolta Medical & Graphic Inc 印刷版材料用樹脂組成物および平版印刷版材料
CN103879169A (zh) * 2012-12-24 2014-06-25 乐凯华光印刷科技有限公司 一种耐uv油墨的阳图热敏ctp版材

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