WO2020080371A1 - Lithographic printing original plate and lithographic printing plate production method - Google Patents

Lithographic printing original plate and lithographic printing plate production method Download PDF

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Publication number
WO2020080371A1
WO2020080371A1 PCT/JP2019/040523 JP2019040523W WO2020080371A1 WO 2020080371 A1 WO2020080371 A1 WO 2020080371A1 JP 2019040523 W JP2019040523 W JP 2019040523W WO 2020080371 A1 WO2020080371 A1 WO 2020080371A1
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group
printing plate
lithographic printing
carbon atoms
resin
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PCT/JP2019/040523
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French (fr)
Japanese (ja)
Inventor
尚志 佐藤
加奈 栢木
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富士フイルム株式会社
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/09Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/095Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having more than one photosensitive layer

Definitions

  • the present disclosure relates to a planographic printing plate precursor and a method for producing a planographic 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 its production for example, those described in Patent Documents 1 to 3 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 3 contains a novolac-type phenol resin and an infrared absorbing dye, and the infrared absorbing dye is a polymer obtained by a graft reaction between an alkali-soluble resin and a low-molecular infrared absorbing dye. Infrared compositions are described.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2006-3658
  • Patent Document 2 Chinese Patent Application Publication No. 1038716969
  • Patent Document 3 Chinese Patent Application Publication No. 101770167
  • the problem to be solved by the embodiments of the present invention is to provide a lithographic printing plate precursor excellent in development latitude and scratch resistance.
  • 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.
  • a lithographic printing plate precursor having an image recording layer on a support, the image recording layer containing an alkali-soluble resin, an infrared absorber having a weight average molecular weight of 4,000 or more, and an onium salt compound.
  • the infrared absorber has an acidic group.
  • the infrared absorber contains a dye structure that absorbs infrared rays and a polymer structure.
  • ⁇ 4> The lithographic printing plate precursor as described in ⁇ 3>, wherein the polymer structure includes a phenol resin structure.
  • ⁇ 5> The lithographic printing plate precursor as described in any one of ⁇ 1> to ⁇ 4>, wherein the image recording layer has an upper layer and a lower layer.
  • ⁇ 6> The onium salt compound described in any one of the above ⁇ 1> to ⁇ 5>, wherein the onium salt compound is at least one compound selected from the group consisting of a quaternary ammonium salt compound and a sulfonium salt compound. The original planographic printing plate.
  • the alkali-soluble resin contains at least one resin selected from the group consisting of acetal resin, phenol resin, acrylic resin, and resin having a urea bond, a urethane bond or an amide bond in the main chain,
  • the lithographic printing plate precursor as described in any one of 1> to ⁇ 6>.
  • R represents an alkyl group or an aryl group.
  • lithographic printing plate precursor as described in any one of ⁇ 1> to ⁇ 8> above, which is a lithographic printing plate precursor for non-silicate development.
  • a method for producing a lithographic printing plate comprising a step of developing using an alkali developer having a pH of 9 or more containing no silicate compound.
  • 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.
  • lithographic printing plate precursor excellent in development latitude and scratch resistance. 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 present disclosure is not limited to such an embodiment.
  • “to” indicating a numerical range is used to mean that numerical values described before and after the numerical range are included as a lower limit value and an upper limit value.
  • the upper limit or the lower limit described in one numerical range may be replaced with the upper limit or the lower limit of the numerical range described in other stages.
  • the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.
  • 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” is described, “R V is an unsubstituted alkyl group, a substituted alkyl group, an unsubstituted aryl group, a substituted aryl group, "Represents an unsubstituted heterocyclic group or a substituted heterocyclic group”.
  • the “main chain” represents the relatively longest binding chain in the molecule of the polymer compound constituting the resin, and the “side chain” represents an atomic group branched from the main chain.
  • the term “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. Moreover, in this indication, “mass%” and “weight%” are synonymous, and “mass part” and “weight part” are synonymous. Further, in the present disclosure, a combination of two or more preferable aspects is a more preferable aspect.
  • 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 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 is an alkali-soluble resin, an infrared absorber having a weight average molecular weight of 4,000 or more (hereinafter, referred to as "specific polymerized”). Also referred to as “infrared absorber”), and onium salt compounds.
  • 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.
  • the lithographic printing plate precursor excellent in development latitude and scratch resistance can be provided by adopting the above-mentioned constitution.
  • the mechanism of action of the excellent effect of the above configuration is not clear, it is estimated as follows.
  • the onium salt compound is an alkali-soluble resin forming the image recording layer, and hydrogen which can be relaxed by heat.
  • the onium salt compound also forms the same interaction with the polymer structure part in the specific polymerized infrared absorber as described above. It is thought that.
  • the specific polymerized infrared absorber generates heat in the vicinity of the onium salt compound, and the interaction between the onium salt and the alkali-soluble resin is efficiently relaxed, and the alkali solubility in the exposed portion is improved. Therefore, it is presumed that the difference in solubility between the exposed portion and the non-exposed portion becomes larger, and the development latitude of the image recording layer (so-called tolerance of developing conditions suitable for image formation) is excellent.
  • the strength of the image recording layer and the scratch resistance are excellent by including the specific polymerized infrared absorber and the onium salt compound in the image recording layer.
  • the image recording layer in the lithographic printing plate precursor according to the present disclosure contains an alkali-soluble resin, an infrared absorber having a weight average molecular weight of 4,000 or more (specific polymerized infrared absorber), and an onium salt compound.
  • the image recording layer in the lithographic printing plate precursor according to the present disclosure contains an alkali-soluble resin.
  • alkali-soluble 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 preferably contains at least one resin selected from the group consisting of an acetal resin, a phenol resin, an acrylic resin, and a resin having a urea bond, a urethane bond or an amide bond in its main chain.
  • the acetal resin is not particularly limited and known resins can be used, and examples thereof include the acetal resins described in paragraphs 0012 to 0021 of International Publication No. 2014/106554.
  • the phenol resin 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, and is preferably a novolak 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 above-mentioned phenol resin is preferably a resol resin.
  • the resole resin include resins obtained by condensing the above-mentioned phenols and aldehydes under basic conditions. The degree of condensation of phenols and formaldehyde, the molecular weight, the residual monomer residual ratio, etc. of the resole resin can be appropriately set according to the purpose.
  • Preferred resole resins include, for example, resole resins obtained from phenol and formaldehyde, resole resins obtained from m-cresol and formaldehyde, resole resins obtained from p-cresol and formaldehyde, resole resins obtained from o-cresol and formaldehyde, Examples thereof include a resole resin obtained from bisphenol A and formaldehyde, a resole resin obtained from 4,4′-bisphenol A and formaldehyde, and the like.
  • a commercial item may be used as the resol resin.
  • Examples of commercially available products are, for example, Sumirite Resin PR-9480, PR-14170, PR-51107, EM-1, PR-EPN, and PR-UFC-504 manufactured by Sumitomo Bakelite Co., Ltd. (Both are trade names), Lekai R-32, etc. (product name) can be used. Further, the resole resin described in JP-B-6-50394 can be used.
  • 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 resin having a urea bond, urethane bond or an amide bond in the main chain has at least one bond of urea bond, urethane bond and amide bond in the main chain from the viewpoint of printing durability of the lithographic printing plate obtained. It is preferable that the main chain has any one of a urea bond and an amide bond, and it is further preferable that the main chain has a urea bond.
  • the resin include polyurea resin, polyurethane resin, polyamide resin and the like.
  • the resin having a urea bond, urethane bond or amide bond in the main chain is not particularly limited as long as it is a conventionally known one, but for example, polyurea resin and polyurethane resin of WO 2015/152209 are preferably used. .
  • As the resin having a urea bond, urethane bond or amide bond in the main chain only one kind may be used, or two or more kinds may be mixed and used.
  • the acrylic resin As the acrylic resin, those known as those used for the image recording layer of the positive type lithographic printing plate precursor can be used without particular limitation.
  • the acrylic resin may be used alone or in combination of two or more.
  • the acrylic resin is preferably a resin in which the content of the constituent unit formed by the (meth) acrylic compound is 50% by mass or more.
  • Examples of the (meth) acrylic compound include alkyl acrylates and alkyl methacrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, benzyl acrylate, methyl methacrylate, ethyl methacrylate, cyclohexyl methacrylate and benzyl methacrylate.
  • Acrylic acid esters and methacrylic acid esters having an aliphatic hydroxyl group such as 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate.
  • Acrylamide or methacrylamide such as acrylamide, methacrylamide, N-methyl acrylamide, N-ethyl acrylamide, N-phenyl acrylamide.
  • Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate.
  • Styrenes such as styrene, ⁇ -methylstyrene, methylstyrene and chloromethylstyrene.
  • nitrogen atom-containing monomers such as N-vinylpyrrolidone, N-vinylpyridine, acrylonitrile and methacrylonitrile.
  • the alkali-soluble resin preferably contains a structural unit derived from an acrylic resin, and a structural unit represented by the following formula 1 and a phenolic hydroxyl group (“phenolic group” in the side chain). Also referred to as a “hydroxy group”).
  • 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 is obtained by at least copolymerizing a maleimide compound and a (meth) acrylamide compound. It is more preferably a copolymer.
  • the alkali-soluble resin preferably has a structural unit represented by the following formula 1.
  • the structural unit represented by the following formula 1 is preferably a structural unit derived from a maleimide compound (a structural 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 Formula 1 is preferably 1 to 20, more preferably 1 to 12, and further preferably 1 to 8. .
  • the number of carbon atoms of the alkyl group represented by R in Formula 1 is preferably 2 or more from the viewpoint of development latitude.
  • the aryl group of R in formula 1 preferably has 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms, and further preferably 6 to 10 carbon atoms.
  • the aryl group represented by R in 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 Formula 1 is preferably an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and an alkyl group having 1 to 12 carbon atoms, Or, an aryl group having 6 to 12 carbon atoms is more preferable, a methyl group, an n-butyl group, a benzyl group, a phenyl group, or a naphthyl group is further preferable, and an n-butyl group, a benzyl group. , Or a phenyl group is particularly preferable, and a phenyl group is most preferable. Further, R in Formula 1 is preferably an aryl group from the viewpoint of development latitude and scratch resistance.
  • alkyl group represented by R in 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 represented by R in Formula 1 examples include a phenyl group and a naphthyl group.
  • Examples of the monomer forming the constitutional unit represented by Formula 1 include N-methylmaleimide, Nn-butylmaleimide, N-benzylmaleimide, N-phenylmaleimide, N-naphthylmaleimide, etc. It is not limited to these.
  • the alkali-soluble resin may have one kind of the structural unit represented by the above formula 1 or two or more kinds.
  • the content of the constitutional unit represented by the above formula 1 (total content in the case of two or more kinds, the same applies below) is based on the total amount 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 preferably has a structural unit having a phenolic hydroxyl group on its side 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 constituent unit having a phenolic hydroxyl group in the side chain preferably has a nitrogen atom from the viewpoint of development latitude and scratch resistance, and is represented by the following formula (Ph-1).
  • the structure is more preferable.
  • 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. From the viewpoint of development latitude and scratch resistance, R ph2 in formula (Ph-1) is preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom.
  • 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 scratch resistance, and is a structural unit represented by the following formula (Ph-2). 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 structural 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, and 10 mol%. % To 60 mol% is more preferable, and 20 mol% to 55 mol% is particularly preferable.
  • the alkali-soluble resin further has a constitutional unit having a cyano group.
  • 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 scratch resistance, and is represented by the following formula (2-2). It is more preferably a structural unit.
  • 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 the cyano group is 1 mol% based on the total amount of the alkali-soluble resin from the viewpoint of development latitude and scratch resistance. It is preferably ⁇ 50 mol%, more preferably 5 mol% to 40 mol%, and particularly preferably 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 viewpoint of developability, development latitude and scratch resistance.
  • 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 mol% with respect to the total amount of the alkali-soluble resin from the viewpoint of development latitude and scratch resistance. It is preferably from 50 to 50 mol%, more preferably from 2 to 40 mol%, 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 mol% based on the total amount of the alkali-soluble resin from the viewpoint of development latitude and scratch resistance. Is preferable, 2 mol% to 40 mol% is more preferable, and 5 mol% to 30 mol% is particularly preferable.
  • 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 absorbing agent (specific polymerized infrared absorbing agent) having a weight average molecular weight of 4,000 or more.
  • the specific polymerized infrared absorber is not particularly limited as long as it is a pigment or dye having a weight average molecular weight of 4,000 or more and absorbing infrared light to generate heat, and various pigments known as infrared absorbers. Alternatively, a dye can be used.
  • the weight average molecular weight of the specific polymerized infrared absorber is preferably 4,000 or more and 50,000 or less, and 6,000 or more and 30,000 or less. More preferably, it is 7,000 or more and 20,000 or less, still more preferably 8,000 or more and 10,000 or less.
  • the specific polymerized infrared absorber preferably has an acidic group, more preferably the polymer structure described below has an acidic group, and further preferably the polymer structure described below has a phenol structure.
  • the acidic group include a phenolic hydroxyl group, a sulfonamide group and an active imide group.
  • the acidic group is preferably a phenolic hydroxyl group or a sulfonamide group.
  • the specific polymerized infrared absorber preferably has a dye structure that absorbs infrared light and a polymer structure.
  • the dye structure that absorbs infrared rays in the specific polymerized infrared absorber include the dye structures of known and commonly used pigments and dyes. Specifically, dyes such as azo dye structure, metal complex azo dye structure, pyrazolone azo dye structure, anthraquinone dye structure, phthalocyanine dye structure, carbonium dye structure, quinoneimine dye structure, methine dye structure, cyanine dye structure, and oxonol dye structure. The structure is mentioned.
  • At least one dye structure selected from the group consisting of a cyanine dye structure, a phthalocyanine dye structure, an oxonol dye structure, a squarylium dye structure, a pyrylium salt dye structure, a thiopyrylium dye structure and a nickel thiolate complex dye structure.
  • a cyanine dye structure is more preferable.
  • a cyanine dye, a ruthenium dye having a halogen atom, etc. described in paragraphs 0016 to 0022 of Chinese Patent Application Publication No. 101770167 may be used.
  • the ruthenium dye is selectively added to the polymer structure part (for example, the polymer main chain of the alkali-soluble resin) included in the specific polymerized infrared absorber. It is believed that the halogen atoms in the ruthenium dye that are bound together promote the dehydrohalogenation reaction.
  • Examples of the polymer structure of the specific polymerized infrared absorber include the polymer structure of the alkali-soluble resin described above.
  • the alkali-soluble resin forming the polymer structure in the specific polymerized infrared absorber is preferably an alkali-soluble resin having an acidic group.
  • the acidic group has the same meaning as the acidic group described above, and the preferred embodiments are also the same. Since the specific polymerized infrared absorber has an acidic group, the acidic group interacts with an onium salt compound described below to reduce the solubility of the exposed area, and the unexposed area has a low solubility in a developing solution. It is presumed that the development latitude increases and the development latitude improves.
  • the alkali-soluble resin is more preferably a phenol resin, further preferably a resol resin.
  • the above-mentioned phenol resin and resol resin have the same meanings as the specific examples of the phenol resin described above, and the preferred embodiments are also the same.
  • the alkali-soluble resin in the specific polymerized infrared absorbing agent preferably has a structural unit represented by the following formula S-1 from the viewpoint of easy graft polymerization reaction.
  • the alkali-soluble resin in the specific polymerized infrared absorber may include two or more kinds of structural units represented by the following formula S-1 in all structural units constituting the alkali-soluble resin.
  • R S1's each independently represent a methylol (CH 2 OH) group or a group represented by the following formula S-2, and R S2's each independently represent an alkyl group or halogen.
  • p1 represents an integer of 1 to 3
  • p2 represents an integer of 0 to 2
  • a wavy line portion represents a bonding position with another structure.
  • L s represents a single bond or an alkylene group
  • R S3 each independently represents an alkyl group or a methylol group
  • p3 represents an integer of 0 to 2
  • the wavy line portion represents Represents a binding site with R S1 in formula S-1.
  • L s is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, and further preferably an alkylene group having 1 to 4 carbon atoms. preferable.
  • R S3 is preferably an alkyl group having 1 to 4 carbon atoms or a methylol group, and more preferably a methylol group.
  • p3 is preferably 1 or 2, and more preferably 2.
  • the position of the OH group in the phenyl group must be at least one position selected from the group consisting of ortho and para positions with respect to the binding site with R S1 in formula S-1. Is preferred, and it is more preferred to have at least the para position.
  • R S2 in the formula S-1 is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and further preferably an alkyl group having 1 or 2 carbon atoms.
  • R S1 in formula S-1 is preferably a methylol group or a group represented by formula S-2.
  • L s is an alkylene group having 1 to 10 carbon atoms (more preferably an alkylene group having 1 to 5 carbon atoms).
  • R S3 is an alkyl group having 1 to 4 carbon atoms or a methylol group (more preferably a methylol group), and as p3 Is preferably 1 or 2 (more preferably 2).
  • P2 in formula S-1 is preferably 0 or 1. It is preferable that p1 in the formula S-1 is 1 or 2. In formula S-1, p1 is preferably 1 and p2 is preferably 1.
  • constituent units contained in the alkali-soluble resin in the specific polymerized infrared absorbent are shown below, but the constituent units contained in the alkali-soluble resin in the specific polymerized infrared absorbent in the present disclosure are not limited thereto. is not.
  • n11 and n12 each independently represent an integer of 1 to 12, and * represents a dye structure that absorbs infrared rays or a bonding portion with another structural unit.
  • the polymer structure and the infrared absorbing dye structure are preferably formed through an ether bond.
  • the specific polymerized infrared absorber is a compound in which the above structure I-1 or structure I-2 and a cyanine dye described later are formed through an ether bond. Is preferred.
  • the dye structure preferably has a side chain of the polymer structure.
  • Specific examples of the specific polymerized infrared absorber include, for example, a compound in which a phenol resin and a cyanine dye are bonded.
  • the content of the dye structure portion that absorbs infrared rays with respect to the specific polymerized infrared absorber is preferably 14% by mass to 75% by mass, and more preferably 25% by mass to 65% by mass.
  • the content of the dye structure portion that absorbs infrared rays with respect to the specific polymerized infrared absorber is 14% by mass or more, the development latitude and scratch resistance are more excellent.
  • the content of the dye structure portion that absorbs infrared rays is 75% by mass or less, the specific polymerized infrared absorbing agent is excellent in alkali solubility, and thus the development dregs suppressing property in the developing solution is more excellent.
  • the specific polymerized infrared absorbers may be used alone or in combination of two or more.
  • the content of the specific polymerized infrared absorber (in the case of containing other infrared absorbers, the total amount) in the image forming layer, from the viewpoint of sensitivity, uniformity of the image forming layer, and durability, It is preferably 0.01% by mass to 50% by mass, more preferably 0.1% by mass to 30% by mass, and 1.0% by mass to 30% by mass with respect to the total mass of the image forming layer. It is particularly preferable that
  • the specific polymerized infrared absorber and the infrared absorber having no polymer structure may be used in combination.
  • pigments in other infrared absorbers commercially available pigments, color index (CI) handbook, “latest pigment handbook” (edited by Japan Pigment Technology Association, published in 1977), “latest pigment application technology” (CMC) Published in 1986) and “Printing Ink Technology” published by CMC, published in 1984).
  • CI color index
  • latest pigment handbook edited by Japan Pigment Technology Association, published in 1977
  • CMC latest pigment application technology
  • Print Ink Technology published by CMC, published in 1984
  • 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. Within the above range, the stability of the pigment dispersion in the heat-sensitive layer coating solution, the uniformity of the heat-sensitive layer, and the like are preferable.
  • 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.
  • a dye is preferably mentioned.
  • infrared absorbers that can be used in the present disclosure, commercially available dyes and known ones described in the 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 gives a high polymerization activity when used in the upper layer of the present disclosure and is excellent in stability and economy.
  • 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.
  • Particularly preferable as the other infrared absorbing agent is the cyanine dye A shown below.
  • the other infrared absorbers may be used alone or in combination of two or more.
  • the content of the other infrared absorbing agent is preferably smaller than the content of the specific polymerized infrared absorbing agent.
  • the specific polymerized infrared absorber can be contained in the upper layer and / or the lower layer.
  • the infrared absorbers of the upper layer and the lower layer may be the same specific polymerized infrared absorber as described above, or may be used in combination with different infrared absorbents, and the specific polymerized infrared absorber may be present in the upper layer. preferable.
  • the content ratio of the specific polymerized infrared absorber and the other infrared absorber is 9: 1 to 1: 9 on a mass basis. Is preferable, and more preferably 8: 2 to 2: 8.
  • the lithographic printing plate precursor according to the present disclosure contains an onium salt compound.
  • the onium salt compound is preferably at least one compound selected from the group consisting of sulfonium salts and quaternary ammonium salt compounds, and is preferably a sulfonium salt compound. Is more preferable.
  • the onium salt compounds may be used alone or in combination of two or more.
  • the sulfonium salt compound is preferably a sulfonium salt 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 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 scratch resistance.
  • An aryl group having 6 to 20 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. It is more preferably 1 to 4 alkyl groups, and particularly preferably a methyl group.
  • 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 scratch resistance.
  • a phenyl group having the above chlorine atom (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 scratch resistance, and the aromatic ring of the aryl group bonded to the sulfur atom has a halogen atom.
  • the compound as a whole is more preferably a triarylsulfonium salt compound having one or more compounds, and is preferably a triarylsulfonium salt compound having an aromatic ring of each of the three aryl groups bonded to a sulfur atom having one or more halogen atoms. More preferably, it is a triarylsulfonium salt compound in which the aromatic ring of each of the three aryl groups bonded to the sulfur atom has at least one chlorine atom.
  • 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.
  • X ⁇ in the formula (S) preferably has an aromatic group from the viewpoint of development latitude and scratch resistance.
  • X ⁇ in the formula (S) preferably has a phenolic hydroxyl group from the viewpoint of development latitude and scratch resistance.
  • X ⁇ in the formula (S) preferably has a diarylketone structure from the viewpoint of development latitude and scratch resistance. Among them, it is particularly preferable that X ⁇ in the formula (S) has a phenolic hydroxyl group and a diarylketone structure from the viewpoint of development latitude and scratch resistance.
  • 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.
  • 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 scratch resistance. It is more preferably 0.5% by mass to 40% by mass, and particularly preferably 1% by mass to 30% by mass.
  • the quaternary ammonium cation in the quaternary ammonium salt compound may be a monovalent cation or a divalent or higher cation having two or more quaternary ammonium structures. Is preferably a monovalent cation.
  • the counter anion in the quaternary ammonium salt compound may be a monovalent anion or a divalent or higher valent anion as long as it is an anion capable of neutralizing the charge, but it is a monovalent anion. Is preferred.
  • the quaternary ammonium cation in the above quaternary ammonium salt compound is preferably a cation represented by the following formula (Am-1), and more preferably a cation represented by the following formula (Am-2).
  • a cation represented by the following formula (Am-3) is particularly preferable.
  • R m1 to R m4 each independently represent a substituent containing at least one carbon atom, and two or more of R m1 to R m4 are bonded to each other to form a ring structure. May be formed.
  • C 1 to C 6 represent carbon atoms
  • N 1 represents a nitrogen atom
  • R 4 to R 17 each independently represent a hydrogen atom or a substituent
  • L 3 represents C 3 and C 4 and a single or double bond linking, or, -C 3 -C 1 -N 1 -C 2 -C 4 - represents a divalent linking group to form a ring structure containing
  • m1 and m2 each independently represents an integer of 0 to 5, and n1 and n2 each independently represent 0 or a positive integer.
  • Examples of the substituent containing at least one carbon atom represented by R m1 to R m4 in formula (Am-1) include the followings.
  • an alkyl group preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, specifically, for example, methyl group, ethyl group, n-butyl.
  • a group preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 8 carbon atoms
  • vinyl group preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 8 carbon atoms
  • alkynyl group preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 12 carbon atoms.
  • aryl group preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, for example, Phenyl group, p-methylphenyl group, naphthyl group, etc.
  • Phenyl group p-methylphenyl group, naphthyl group, etc.
  • substituents may be further substituted. When there are two or more substituents, they may be the same or different. If possible, they may be linked to each other to form a ring.
  • R m1 to R m4 in formula (Am-1) are preferably an alkyl group, an aryl group, or a group in which any of these is further substituted.
  • the total carbon number of R m1 to R m4 is preferably 8 to 80, more preferably 10 to 64, and 12 to 48. It is particularly preferable that
  • Examples of the substituent in R 4 to R 17 of the formula (Am-2) include the followings.
  • an alkyl group preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, specifically, for example, methyl group, ethyl group, n-butyl.
  • alkenyl preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, specifically, for example, methyl group, ethyl group, n-butyl.
  • a group preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 8 carbon atoms
  • vinyl group preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 8 carbon atoms
  • alkynyl group preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 12 carbon atoms.
  • examples thereof include a propargyl group, a 3-pentynyl group, etc.), an aryl group (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms, for example, Phenyl group, p-methylphenyl group, naphthyl group, etc.),
  • An amino group preferably having 0 to 20 carbon atoms, more preferably 0 to 12 carbon atoms, particularly preferably 0 to 6 carbon atoms, for example, amino group, methylamino group, dimethylamino group, diethylamino group, diphenylamino group, A dibenzylamino group, etc.
  • an alkoxy group preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms
  • a methoxy group preferably having 0 to 20 carbon atoms, more preferably 0 to 12 carbon atoms, particularly preferably 0 to 6 carbon atoms
  • an alkoxy group preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms
  • an aryloxy group (preferably having 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms), for example, a phenyloxy group, a 2-naphthyloxy group. Etc.),
  • Acyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include an acetyl group, a benzoyl group, a formyl group, a pivaloyl group).
  • Alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, and examples thereof include a methoxycarbonyl group and an ethoxycarbonyl group), aryloxycarbonyl.
  • a group (preferably having 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, particularly preferably 7 to 10 carbon atoms, and examples thereof include a phenyloxycarbonyl group); an acyloxy group (preferably having 2 carbon atoms). To 20, more preferably 2 to 16 carbon atoms, and particularly preferably 2 to 10 carbon atoms, such as an acetoxy group, And an acylamino group (preferably having a carbon number of 2 to 20, more preferably a carbon number of 2 to 16, and particularly preferably a carbon number of 2 to 10) such as an acetylamino group and a benzoylamino group. Can be mentioned.),
  • Alkoxycarbonylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, and examples thereof include a methoxycarbonylamino group) and an aryloxycarbonylamino group.
  • Sulfonylamino group (preferably having carbon number 1 to 20, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms, and examples thereof include a methanesulfonylamino group and a benzenesulfonylamino group.),
  • a sulfamoyl group (preferably having a carbon number of 0 to 20, more preferably 0 to 16 carbon atoms, particularly preferably 0 to 12 carbon atoms, for example Rufamoiru group, methylsulfamoyl group, dimethylsulfamoyl group, and a phenylsulfamoyl group.)
  • Carbamoyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include a carbamoyl group, a methylcarbamoyl group, a diethylcarbamoyl group and a phenylcarbamoyl group.
  • An alkylthio group (preferably having a carbon number of 1 to 20, more preferably a carbon number of 1 to 16, and particularly preferably a carbon number of 1 to 12, and examples thereof include a methylthio group and an ethylthio group), an arylthio group ( It preferably has 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, and particularly preferably 6 to 12 carbon atoms, and examples thereof include a phenylthio group.), A sulfonyl group (preferably 1 to 20 carbon atoms, more preferably It preferably has 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include a mesyl group and a tosyl group.
  • a sulfinyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms, and examples thereof include a methanesulfinyl group and a benzenesulfinyl group).
  • a ureido group (preferably having a carbon number of 1 to 20, more preferably a carbon number of 1 to 16 and particularly preferably a carbon number of 1 to 12, and examples thereof include a ureido group, a methylureido group, a phenylureido group, etc.),
  • Phosphoric acid amide group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include a diethylphosphoric acid amide group and a phenylphosphoric acid amide group.
  • Hydroxy group for example, fluorine atom, chlorine atom, bromine atom, iodine atom
  • cyano group for example, fluorine atom, chlorine atom, bromine atom, iodine atom
  • sulfo group carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group
  • Heterocyclic group preferably having 1 to 30 carbon atoms, more preferably having 1 to 12 carbon atoms, and the hetero atom includes, for example, a nitrogen atom, an oxygen atom and a sulfur atom, and specifically, for example, imidazolyl.
  • substituents may be further substituted. When there are two or more substituents, they may be the same or different. If possible, they may be linked to each other to form a ring.
  • the substituent in R 4 to R 17 of formula (Am-2) is preferably an alkyl group, an aryl group, an alkenyl group, an alkynyl group, or a group in which any of these is further substituted.
  • R 4 to R 17 in formula (Am-2) may be the same or different, and may combine with each other to form a ring structure.
  • R 4 to R 17 may be bonded to L 3 or R 4 to R 17 , respectively, to form a ring structure.
  • R 4 to R 11 are accordingly absent. Good.
  • N1 and n2 in formula (Am-2) are each independently preferably 0, 1, 2 or 3, more preferably 0, 1 or 2, and particularly preferably 0 or 1.
  • a plurality of R 12 and R 13 , and R 15 and R 16 may be the same or different, and are bonded to each other to form a ring structure. May be.
  • Preferable examples of the divalent linking group for L 3 in the formula (Am-2) include —O—, —S—, —N (R L1 ) —, and —C (R L2 ) (R L3 ) —.
  • R L1 to R L3 include a hydrogen atom or a substituent in R 4 to R 17 , which may be bonded to any of R 4 to R 14 to form a ring structure. When C 3 and C 4 and L 3 form a double bond, R L1 to R L3 may not be present.
  • the quaternary ammonium cation in the above quaternary ammonium salt compound preferably has an aromatic ring from the viewpoint of development latitude, scratch resistance and chemical resistance of the lithographic printing plate obtained.
  • the quaternary ammonium cation and the counter anion in the quaternary ammonium salt compound each preferably have an aromatic ring from the viewpoint of development latitude, scratch resistance, and chemical resistance of the lithographic printing plate obtained.
  • the quaternary ammonium cation in the quaternary ammonium salt compound preferably has an alicyclic structure from the viewpoint of development latitude, scratch resistance and chemical resistance of the resulting lithographic printing plate, and has a nitrogen atom.
  • the aliphatic ring is preferably a 5-membered ring to an 8-membered ring, more preferably a 5-membered ring or a 6-membered ring, and particularly preferably a 6-membered ring.
  • the quaternary ammonium cation in the quaternary ammonium salt compound has an aromatic ring and an aliphatic ring from the viewpoints of development latitude, scratch resistance and chemical resistance of the lithographic printing plate obtained.
  • the counter anion in the quaternary ammonium salt compound from the viewpoint of development latitude, scratch resistance and chemical resistance of the lithographic printing plate obtained, sulfonate ion, carboxylate ion, inorganic acid ion having a halogen atom, or, A halide ion is preferable, a sulfonate ion, an inorganic acid ion having a halogen atom, or a halide ion is more preferable, and a sulfonate ion is particularly preferable.
  • the counter anion in the quaternary ammonium salt compound preferably has an aromatic group from the viewpoint of development latitude, scratch resistance, and chemical resistance of the lithographic printing plate obtained.
  • the counter anion in the quaternary ammonium salt compound preferably has a phenolic hydroxyl group from the viewpoint of development latitude, scratch resistance and chemical resistance of the lithographic printing plate obtained.
  • the counter anion in the quaternary ammonium salt compound preferably has a diarylketone structure from the viewpoint of development latitude, scratch resistance and chemical resistance of the lithographic printing plate obtained.
  • the counter anion in the quaternary ammonium salt compound particularly preferably has a phenolic hydroxyl group and a diarylketone structure from the viewpoints of development latitude, scratch resistance, and chemical resistance of the lithographic printing plate obtained.
  • the pKa (acid dissociation constant) of the conjugate acid (XH) of the counter anion in the quaternary ammonium salt compound is preferably less than 5, more preferably -10 or more and less than 5, and more preferably -10 or more. It is particularly preferably 2 or less.
  • 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.
  • the counter anion in the quaternary ammonium salt compound include chloride ion, bromide ion, iodide ion, BF 4 ⁇ , PF 6 ⁇ , trifluoromethanesulfonate ion, p-toluenesulfonate ion, methanesulfone.
  • An acid ion or 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 quaternary ammonium salt compounds may be used alone or in combination of two or more.
  • the content of the quaternary ammonium salt compound is 0.1% by mass to 50% by mass based on the total mass of the image recording layer from the viewpoint of development latitude, scratch resistance and chemical resistance of the lithographic printing plate obtained. %, More preferably 0.5% by mass to 40% by mass, and particularly preferably 1% by mass to 30% by mass.
  • the quaternary ammonium cation in the quaternary ammonium salt compound may be a monovalent cation or a divalent or higher cation having two or more quaternary ammonium structures, but it is a monovalent cation. It is preferable.
  • the counter anion in the quaternary ammonium salt compound may be a monovalent anion or a divalent or higher valent anion as long as it is an anion capable of neutralizing the charge, but it is a monovalent anion. Is preferred.
  • the onium salt compound according to the present disclosure may be an onium salt compound other than the above quaternary ammonium salt compound and sulfonium salt compound (hereinafter, also referred to as “other onium compound”).
  • onium salt compounds include diazonium salt compounds, iodonium salt compounds, pyridinium salt compounds, and azinium salt compounds.
  • other onium salt compounds include known diazonium salts, iodonium salts, primary to tertiary ammonium salts, pyridinium salts, azinium salts, and the like. Among them, triarylsulfonium or diaryliodonium sulfonates.
  • 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.
  • onium salt compounds include the following compounds (PAG-4) or (PAG-5).
  • Me represents a methyl group.
  • 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.
  • the other resin the above-mentioned phenol resin is preferably used.
  • the phenol resin in the other resins has the same meaning as the above-mentioned phenol resin, and the preferred embodiments are also the same.
  • the content of the other resin in the image recording layer in the present disclosure is preferably 90 parts by mass or less based on 100 parts by mass of the total content of the alkali-soluble resin, from the viewpoint of burning suitability and image forming property.
  • the amount is 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 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.
  • These dyes are preferably added in an amount of 0.01% by mass to 10% by mass, more preferably 0.1% by mass to 3% by mass, based on the total mass of the image recording layer. .
  • 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 addition amount 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, the specific polymerized infrared absorber, and the onium salt compound may be contained in either the lower layer or the upper layer, but from the viewpoint of printing durability and scratch resistance, the upper layer has a specific height. It is preferable that at least the molecularized infrared absorber and the onium salt compound are contained, and that the lower layer contains at least an alkali-soluble resin.
  • 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 .
  • 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, 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, for example, an automatic developing device solution.
  • 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 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 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 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.
  • Examples 1-1 to 13-1 and Comparative Examples 1-1 and 2-1 ⁇ Formation of image recording layer (multilayer)>
  • the web-shaped substrate thus obtained was coated with a lower layer coating solution having the following composition by a bar coater so that the coating amount was 0.85 g / m 2 , followed by drying at 160 ° C. for 44 seconds and immediately cooling with cold air at 17 ° C.-20 ° C. It was cooled until the temperature of the support reached 35 ° C.
  • a coating solution for the upper layer having the following composition was applied by a bar coater to a coating amount of 0.22 g / m 2 , dried at 148 ° C. for 25 seconds, and then gradually cooled by a wind at 20 ° C. to 26 ° C.
  • the lithographic printing plate precursors of Examples and Comparative Examples were produced.
  • Polymer 1 0.015 part Polymer 2 (polymer shown below): 0.00328 part Onium salt compound consisting of cation and anion described in Table 1: Addition amount described in Table 1 (for example, Example 1 -1 is 0.08 copies.) -Surfactant (Megafac F-780F, manufactured by DIC Corporation: 0.008 parts) -Methyl ethyl ketone: 6.79 parts-1-Methoxy-2-propanol: 13.07 parts
  • Example 1-2 to Example 13-2 and Comparative Examples 1-2 and 2-2 On the support obtained in the same manner as in Example 1-1, a single-layer coating solution having the following composition was applied to give a coating amount of 1.2 g / m 2, and dried to form a recording layer.
  • the lithographic printing plate precursors of Example 1-2 to Example 13-2 and Comparative Examples 1-2 and 2-2 were obtained.
  • the development ratio is adjusted by changing the dilution ratio of the developing solution to adjust the conductivity, the image area is not eluted, and there is no stain or coloration due to the poorly developed photosensitive layer residual film.
  • the difference (mS / cm) between the maximum value of conductivity and the minimum value of conductivity (hereinafter, also referred to as “conductivity difference”) is used as the development latitude, and the following evaluation criteria are used.
  • the evaluation was performed according to. It can be said that the higher the evaluation score, the better the development latitude, and the evaluation score of 3 or more, the better the development latitude.
  • lithographic printing plate precursor thus obtained was conditioned for 2 hours in an environment of 25 ° C. and 60% RH, punched out into 2.5 cm ⁇ 2.5 cm, and manufactured by Shinto Kagaku Co., Ltd. as a continuous load type scratch strength tester TYPE. Mounted on -18, set so that the back surface of the punched lithographic printing plate precursor comes into contact with the front surface of the lithographic printing plate precursor that has not been punched out, and lithographically plate it at a pressure of 0 gf to 1,500 gf (0N to 14.7N). Several parts of the printing plate precursor were scratched and scratched.
  • the lithographic printing plate precursor with scratches was set on the Trendsetter 3244 manufactured by Creo, and the output was 7 W at the resolution of 2,400 dpi (dot per inch, 1 inch was 2.54 cm), the outer surface drum rotation speed was 150 rpm (revolutions per minute), and the plate surface energy was set. Image exposure was performed at 110 mJ / cm 2 .
  • the lithographic printing plate precursor after image exposure was mounted on an offset rotary printing machine manufactured by Tokyo Kikai Seisakusho, and Soybee KKST-S (red) manufactured by Inktec Co., Ltd.
  • a test pattern containing an FM screen chart of 175 lpi (lines per inch) / 2400 dpi with a dot area ratio of 1% to 99% was imagewise drawn (exposed).
  • the lithographic printing plate precursors of Examples and Comparative Examples were manufactured by Fuji Film Co., Ltd., which was prepared by using Developer XP-D developer (diluted to have an electric conductivity of 43 mS / cm, pH 13.1). Development was performed using a PS processor LP940H at a development temperature of 30 ° C. and a development time of 12 seconds.
  • the developer replenisher XP-DR manufactured by FUJIFILM Corporation was used to replenish the developer with an automatic replenishment system.
  • the halftone dot area ratio (%) of the FM screen 50% halftone dots on the plate was measured using iCPlate2 manufactured by X-RITE, and 50% halftone dots during continuous treatment were measured.
  • the difference between the maximum value and the minimum value of the dot area ratio (%) of the dots was obtained and evaluated according to the following evaluation criteria. The higher the evaluation score is, the smaller the difference of 50% halftone dot reproduction is, and the better the processing stability is.
  • the structural unit a in Table 1 and Table 2 represents the structural unit represented by the above formula 1, and the structural unit b represents the structural unit having a phenolic hydroxyl group in the side chain.
  • the composition ratios (mol ratios) of the alkali-soluble resins shown in Tables 1 and 2 are listed in order from the structural units shown on the left of Tables 1 and 2, and, for example, in Example 1-1.
  • A-1 is 28 mol%
  • b-1 is 26 mol%
  • c-1 is 20 mol%
  • c-2 6 mol%
  • c-3 is 20 mol%.
  • a-1 Structural unit shown below
  • the alkali-soluble resin used in the synthesis of the specific IR dye (1) is a resole resin containing a constitutional unit represented by the structural formula II shown below: RM-1 (manufactured by Lekai, methylol compound of m-cresol resin). Was used. A solution was prepared by dissolving 100 g of the above RM-1 in 400 mL of N, N-dimethylformamide, and at 40 ° C., 0.2 g of sodium hydroxide was slowly added to the solution, and the obtained reaction product was added for 30 minutes. It was stirred.
  • RM-1 manufactured by Lekai, methylol compound of m-cresol resin
  • R represents a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryl group, or a halogen atom, and m and n each independently represent an integer of 1 to 12.
  • the alkali-soluble resin used for the synthesis of the specific IR dye (2) is a compound represented by the above-mentioned structural formula I-1: BTB-29 (a methylol compound of m-cresol resin manufactured by Weihai Amagi Chemical Co., Ltd.). Was used. A solution was prepared by dissolving BTB-29 in 400 mL of N, N-dimethylformamide. At 40 ° C., 0.2 g sodium hydroxide was slowly added to the solution and the reaction was stirred for 30 minutes.
  • Cyanine dye A the following compound
  • the developer DP-4 (containing silicate) manufactured by Fuji Film Co., Ltd. Development was carried out at a development time of 25 seconds using a PS processor LP940H manufactured by FUJIFILM Corporation, which was prepared by doubling the dilution.
  • the lithographic printing plate precursor of the example which is the lithographic printing plate precursor according to the present disclosure, was excellent in development latitude and scratch resistance as compared with the lithographic printing plate precursor of Comparative Example. It can be seen that a lithographic printing plate can be obtained. Further, it can be seen that the lithographic printing plate precursor of the example which is the lithographic printing plate precursor according to the present disclosure can provide a lithographic printing plate excellent in processing stability.

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Abstract

This lithographic printing original plate has an image recording layer on a support, wherein the image recording layer contains, an alkali-soluble resin, an infrared ray absorbing agent having a weight average molecular weight not less than 4,000, and onium salt compound. This lithographic printing plate production method uses said lithographic printing original plate.

Description

平版印刷版原版、及び、平版印刷版の作製方法Lithographic printing plate precursor and method of making lithographic printing plate
 本開示は、平版印刷版原版、及び、平版印刷版の作製方法に関する。 The present disclosure relates to a planographic printing plate precursor and a method for producing a planographic printing plate.
 一般に平版印刷版は、印刷過程でインキを受容する親油性の画像部と湿し水を受容する親水性の非画像部とからなる。
 平版印刷は、水と油性インキとが互いに反発する性質を利用して、平版印刷版の親油性の画像部をインキ受容部、親水性の非画像部を湿し水受容部(インキ非受容部)として、平版印刷版の表面にインキの付着性の差異を生じさせ、画像部のみにインキを着肉させた後、紙等の被印刷体にインキを転写して印刷する方法である。
 現在、平版印刷版原版から平版印刷版を作製する製版工程においては、CTP(コンピュータトゥプレート)技術による画像露光が行われている。即ち、画像露光は、レーザーやレーザーダイオードを用いて、リスフィルムを介することなく、直接平版印刷版原版に走査露光などにより行われる。
 従来の平版印刷版原版、又は、その製造に用いられる感光性樹脂組成物としては、例えば、特許文献1~3に記載されたものが知られている。
Generally, 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). ) Is a method in which a difference in ink adhesion is caused on the surface of the lithographic printing plate, the ink is applied only to the image area, and then the ink is transferred to a printing medium such as paper for printing.
Currently, in a plate making process for producing a lithographic printing plate from a lithographic printing plate precursor, 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.
As a conventional lithographic printing plate precursor or a photosensitive resin composition used for its production, for example, those described in Patent Documents 1 to 3 are known.
 特許文献1には、支持体上に、樹脂及び赤外線吸収剤を含み、赤外レーザー露光によりアルカリ水溶液に対する溶解性が増大するポジ型記録層を少なくとも2層以上有する平版印刷版原版であって、上記ポジ型記録層のうち支持体に最も近接するポジ型記録層が、少なくとも2種の樹脂を含有し、それらの樹脂の少なくとも1種が分散相を形成しており、且つ、上記樹脂の少なくとも1種がマレイミドを含むポリマーであることを特徴とする平版印刷版原版が記載されている。 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.
 特許文献2には、支持体上に、マレイミド構造を有する3元~5元共重合体及び赤外線吸収剤を含む画像記録層を有し、上記共重合体の重量平均分子量が15,000~35,000であり、かつ数平均分子量が7,000~15,000である平版印刷版原版が記載されている。 In 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.
 特許文献3には、ノボラック型フェノール樹脂及び赤外線吸収色素を含み、赤外線吸収色素が、アルカリ可溶性樹脂と低分子の赤外線吸収色素とのグラフト反応により得られる重合体であることを特徴とするポジ型赤外線組成物が記載されている。 Patent Document 3 contains a novolac-type phenol resin and an infrared absorbing dye, and the infrared absorbing dye is a polymer obtained by a graft reaction between an alkali-soluble resin and a low-molecular infrared absorbing dye. Infrared compositions are described.
  特許文献1: 特開2006-3658号公報
  特許文献2:中国特許出願公開第103879169号明細書
  特許文献3: 中国特許出願公開第101770167号明細書
Patent Document 1: Japanese Patent Application Laid-Open No. 2006-3658 Patent Document 2: Chinese Patent Application Publication No. 1038716969 Patent Document 3: Chinese Patent Application Publication No. 101770167
 本発明の実施形態が解決しようとする課題は、現像ラチチュード及び耐キズ性に優れる平版印刷版原版を提供することである。
 本発明の他の実施形態が解決しようとする課題は、上記平版印刷版原版を用いた平版印刷版の作製方法を提供することである。
The problem to be solved by the embodiments of the present invention is to provide a lithographic printing plate precursor excellent in development latitude and scratch resistance.
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.
 上記課題を解決するための手段には、以下の態様が含まれる。
<1> 支持体上に画像記録層を有し、上記画像記録層が、アルカリ可溶性樹脂、重量平均分子量4,000以上の赤外線吸収剤、及びオニウム塩化合物を含む、平版印刷版原版。
<2> 上記赤外線吸収剤が、酸性基を有する、上記<1>に記載の平版印刷版原版。
<3> 上記赤外線吸収剤が、赤外線を吸収する色素構造とポリマー構造とを含む、上記<1>又は<2>に記載の平版印刷版原版。
<4> 上記ポリマー構造が、フェノール樹脂構造を含む、上記<3>に記載の平版印刷版原版。
<5> 上記画像記録層が、上層及び下層を有する、上記<1>~<4>のいずれか1つに記載の平版印刷版原版。
<6> 上記オニウム塩化合物が、第4級アンモニウム塩化合物、及び、スルホニウム塩化合物よりなる群から選ばれる少なくとも1種の化合物である、上記<1>~<5>のいずれか1つに記載の平版印刷版原版。
<7> 上記アルカリ可溶性樹脂が、アセタール樹脂、フェノール樹脂、アクリル樹脂、及び、ウレア結合、ウレタン結合又はアミド結合を主鎖に有する樹脂よりなる群から選ばれる少なくとも1種の樹脂を含む、上記<1>~<6>のいずれか1つに記載の平版印刷版原版。
<8> 上記アルカリ可溶性樹脂が、下記式1で表される構成単位と、側鎖にフェノール性水酸基を有する構成単位と、を有する、上記<1>~<7>のいずれか1つに記載の平版印刷版原版。
Means for solving the above problems include the following aspects.
<1> A lithographic printing plate precursor having an image recording layer on a support, the image recording layer containing an alkali-soluble resin, an infrared absorber having a weight average molecular weight of 4,000 or more, and an onium salt compound.
<2> The lithographic printing plate precursor as described in <1> above, wherein the infrared absorber has an acidic group.
<3> The lithographic printing plate precursor as described in <1> or <2> above, wherein the infrared absorber contains a dye structure that absorbs infrared rays and a polymer structure.
<4> The lithographic printing plate precursor as described in <3>, wherein the polymer structure includes a phenol resin structure.
<5> The lithographic printing plate precursor as described in any one of <1> to <4>, wherein the image recording layer has an upper layer and a lower layer.
<6> The onium salt compound described in any one of the above <1> to <5>, wherein the onium salt compound is at least one compound selected from the group consisting of a quaternary ammonium salt compound and a sulfonium salt compound. The original planographic printing plate.
<7> The alkali-soluble resin contains at least one resin selected from the group consisting of acetal resin, phenol resin, acrylic resin, and resin having a urea bond, a urethane bond or an amide bond in the main chain, The lithographic printing plate precursor as described in any one of 1> to <6>.
<8> The alkali-soluble resin described in any one of <1> to <7>, wherein the alkali-soluble resin has a structural unit represented by the following formula 1 and a structural unit having a phenolic hydroxyl group in a side chain. The original planographic printing plate.
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
 式1中、Rは、アルキル基又はアリール基を表す。 In Formula 1, R represents an alkyl group or an aryl group.
<9> ノンシリケート現像用平版印刷版原版である上記<1>~<8>のいずれか1つに記載の平版印刷版原版。
<10> 上記<1>~<9>のいずれか1つに記載の平版印刷版原版を赤外線レーザーを用いて画像様に露光する工程、及び、
 シリケート化合物を含まないpH9以上のアルカリ現像液を用いて現像する工程を含む
 平版印刷版の作製方法。
<11> 上記アルカリ現像液の液活性を、上記アルカリ現像液の電導度で測定し、測定された測定値に従って補充液を加えて、目標の電導度となるように調整し、液活性を制御する工程を含む上記<10>に記載の平版印刷版の作製方法。
<9> The lithographic printing plate precursor as described in any one of <1> to <8> above, which is a lithographic printing plate precursor for non-silicate development.
<10> A step of imagewise exposing the lithographic printing plate precursor according to any one of <1> to <9> above, using an infrared laser, and
A method for producing a lithographic printing plate, comprising a step of developing using an alkali developer having a pH of 9 or more containing no silicate compound.
<11> 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> above, which comprises the step of:
 本発明の実施形態によれば、現像ラチチュード及び耐キズ性に優れる平版印刷版原版を提供することができる。
 また、本発明の他の実施形態によれば、上記平版印刷版原版を用いた平版印刷版の作製方法を提供することができる。
According to the embodiment of the present invention, it is possible to provide a lithographic printing plate precursor excellent in development latitude and scratch resistance.
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.
支持体の作製に用いられる機械的粗面化装置一例を示す概略構成図である。It is a schematic block diagram which shows an example of the mechanical roughening apparatus used for manufacture of a support body. 支持体の作製に用いられる電気化学的粗面化に用いる交番波形電流波形図の一例を示すグラフである。It is a graph which shows an example of the alternating waveform current waveform diagram used for electrochemical roughening used for manufacture of a support body. 支持体の作製に用いられる電気化学的粗面化に用いる2つ以上のラジアルドラムローラを連結した装置の概略構成図である。It is a schematic block diagram of the apparatus which connected two or more radial drum rollers used for electrochemical roughening used for manufacture of a support body. 支持体の作製に適用可能な二段給電電解法における電解処理装置の概略図である。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.
 以下において、本開示の内容について詳細に説明する。以下に記載する構成要件の説明は、本開示の代表的な実施態様に基づいてなされることがあるが、本開示はそのような実施態様に限定されるものではない。
 なお、本開示において、数値範囲を示す「~」とはその前後に記載される数値を下限値及び上限値として含む意味で使用される。
 本開示中に段階的に記載されている数値範囲において、一つの数値範囲で記載された上限値又は下限値は、他の段階的な記載の数値範囲の上限値又は下限値に置き換えてもよい。また、本開示中に記載されている数値範囲において、その数値範囲の上限値又は下限値は、実施例に示されている値に置き換えてもよい。
 更に、本開示において組成物中の各成分の量は、組成物中に各成分に該当する物質が複数存在する場合、特に断らない限り、組成物中に存在する該当する複数の物質の合計量を意味する。
The details of the present disclosure will be described below. The description of the constituent elements described below may be made based on the representative embodiment of the present disclosure, but the present disclosure is not limited to such an embodiment.
In the present disclosure, “to” indicating a numerical range is used to mean that numerical values described before and after the numerical range are included as a lower limit value and an upper limit value.
In the numerical ranges described stepwise in the present disclosure, the upper limit or the lower limit described in one numerical range may be replaced with the upper limit or the lower limit of the numerical range described in other stages. . Further, in the numerical range described in the present disclosure, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.
Further, in the present disclosure, 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. Means
 また、本開示における基(原子団)の表記において、置換及び無置換を記していない表記は、置換基を有さないものと共に置換基を有するものをも包含するものである。例えば「アルキル基」とは、置換基を有さないアルキル基(無置換アルキル基)のみならず、置換基を有するアルキル基(置換アルキル基)をも包含するものである。
 本開示において、「(メタ)アクリル」は、アクリル及びメタクリルの両方を包含する概念で用いられる語であり、「(メタ)アクリロイル」は、アクリロイル及びメタクリロイルの両方を包含する概念として用いられる語である。
 また、本開示において、式で表される化合物における基の表記に関して、置換又は無置換を記していない場合、その基がさらに置換基を有することが可能な場合には、他に特に規定がない限り、その基は、無置換の基のみならず、置換基を有する基も包含する。例えば、式において、「Rはアルキル基、アリール基又は複素環基を表す」との記載があれば、「Rは無置換アルキル基、置換アルキル基、無置換アリール基、置換アリール基、無置換複素環基又は置換複素環基を表す」ことを意味する。
 本開示において、「主鎖」とは樹脂を構成する高分子化合物の分子中で相対的に最も長い結合鎖を表し、「側鎖」とは主鎖から枝分かれしている原子団を表す。
In addition, in the notation of a group (atomic group) in the present disclosure, the notation that does not indicate substituted and unsubstituted includes not only those having no substituent but also those having a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present disclosure, “(meth) acrylic” is a term used as a concept including both acryl and methacryl, and “(meth) acryloyl” is a term used as a concept including both acryloyl and methacryloyl. is there.
Further, in the present disclosure, with respect to the notation of 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. For example, in the formula, if “R V represents an alkyl group, an aryl group or a heterocyclic group” is described, “R V is an unsubstituted alkyl group, a substituted alkyl group, an unsubstituted aryl group, a substituted aryl group, "Represents an unsubstituted heterocyclic group or a substituted heterocyclic group".
In the present disclosure, the “main chain” represents the relatively longest binding chain in the molecule of the polymer compound constituting the resin, and the “side chain” represents an atomic group branched from the main chain.
 また、本開示中の「工程」の用語は、独立した工程だけではなく、他の工程と明確に区別できない場合であっても、その工程の所期の目的が達成されれば本用語に含まれる。
 また、本開示において、「質量%」と「重量%」とは同義であり、「質量部」と「重量部」とは同義である。
 更に、本開示において、2以上の好ましい態様の組み合わせは、より好ましい態様である。
 また、本開示における重量平均分子量(Mw)及び数平均分子量(Mn)は、特に断りのない限り、TSKgel GMHxL、TSKgel G4000HxL、TSKgel G2000HxL(何れも東ソー(株)製の商品名)のカラムを使用したゲルパーミエーションクロマトグラフィ(GPC)分析装置により、溶媒THF(テトラヒドロフラン)、示差屈折計により検出し、標準物質としてポリスチレンを用いて換算した分子量である。
 本開示において、全固形分量とは、組成物における溶剤等の揮発性成分を除いた成分の全質量をいう。
 本開示において、「平版印刷版原版」の用語は、平版印刷版原版だけでなく、捨て版原版を包含する。また、「平版印刷版」の用語は、平版印刷版原版を、必要により、露光、現像などの操作を経て作製された平版印刷版だけでなく、捨て版を包含する。捨て版原版の場合には、必ずしも、露光、現像の操作は必要ない。なお、捨て版とは、例えばカラーの新聞印刷において一部の紙面を単色又は2色で印刷を行う場合に、使用しない版胴に取り付けるための平版印刷版原版である。
 以下、本開示を詳細に説明する。
In addition, the term “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.
Moreover, in this indication, "mass%" and "weight%" are synonymous, and "mass part" and "weight part" are synonymous.
Further, in the present disclosure, a combination of two or more preferable aspects is a more preferable aspect.
In addition, 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.
In the present disclosure, the total solid content refers to the total mass of components excluding volatile components such as a solvent in the composition.
In the present disclosure, the term “lithographic printing plate precursor” includes not only the lithographic printing plate precursor but also the discarded plate precursor. In addition, 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.
Hereinafter, the present disclosure will be described in detail.
(平版印刷版原版)
 本開示に係る平版印刷版原版は、支持体上に画像記録層を有し、上記画像記録層が、アルカリ可溶性樹脂、重量平均分子量4,000以上の赤外線吸収剤(以下、「特定高分子化赤外線吸収剤」ともいう。)、及びオニウム塩化合物を含む。
(Lithographic printing plate original)
The lithographic printing plate precursor according to the present disclosure has an image recording layer on a support, and the image recording layer is an alkali-soluble resin, an infrared absorber having a weight average molecular weight of 4,000 or more (hereinafter, referred to as "specific polymerized"). Also referred to as "infrared absorber"), and onium salt compounds.
 また、本開示に係る平版印刷版原版は、ポジ型平版印刷版原版であり、サーマルポジ型平版印刷版原版であることが好ましい。
 更に、本開示に係る平版印刷版原版は、ノンシリケート現像用平版印刷版原版として好適に用いることができる。
Further, 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.
 本発明者らが鋭意検討した結果、上記構成をとることにより、現像ラチチュード及び耐キズ性に優れる平版印刷版原版を提供できることを見出した。
 上記構成による優れた効果の作用機構は明確ではないが、以下のように推定している。
 上記画像記録層において、特定高分子化赤外線吸収剤とオニウム塩化合物とを含むことにより、未露光部において、オニウム塩化合物は、画像記録層を形成するアルカリ可溶性樹脂と、熱によって緩和可能な水素結合及びイオン結合等の相互作用を形成して、アルカリ溶解性を低下させるだけでなく、オニウム塩化合物は特定高分子化赤外線吸収剤中の高分子構造部分と、上記と同様の相互作用を形成すると考えられる。
 一方、露光部では、オニウム塩化合物の近傍において特定高分子化赤外線吸収剤が発熱し、オニウム塩とアルカリ可溶性樹脂との相互作用が効率的に緩和されて、露光部にアルカリ溶解性が向上するため、露光部と非露光部との溶解性の差がより大きくなり、上記画像記録層の現像ラチチュード(いわゆる、画像形成に適する現像条件の許容性)に優れると推定している。
 また、画像記録層中に特定高分子化赤外線吸収剤とオニウム塩化合物とを含むことにより、画像記録層の強度により優れ、耐キズ性にも優れると推察される。
As a result of diligent studies by the present inventors, it has been found that the lithographic printing plate precursor excellent in development latitude and scratch resistance can be provided by adopting the above-mentioned constitution.
Although the mechanism of action of the excellent effect of the above configuration is not clear, it is estimated as follows.
In the image recording layer, by containing the specific polymerized infrared absorber and the onium salt compound, in the unexposed portion, the onium salt compound is an alkali-soluble resin forming the image recording layer, and hydrogen which can be relaxed by heat. Not only does it form an interaction such as a bond or an ionic bond to lower the alkali solubility, but the onium salt compound also forms the same interaction with the polymer structure part in the specific polymerized infrared absorber as described above. It is thought that.
On the other hand, in the exposed portion, the specific polymerized infrared absorber generates heat in the vicinity of the onium salt compound, and the interaction between the onium salt and the alkali-soluble resin is efficiently relaxed, and the alkali solubility in the exposed portion is improved. Therefore, it is presumed that the difference in solubility between the exposed portion and the non-exposed portion becomes larger, and the development latitude of the image recording layer (so-called tolerance of developing conditions suitable for image formation) is excellent.
In addition, it is presumed that the strength of the image recording layer and the scratch resistance are excellent by including the specific polymerized infrared absorber and the onium salt compound in the image recording layer.
 また、本開示に係る平版印刷版の製造方法において、シリケート化合物を含まない現像液を用いるため、シリケートカスの抑制に優れやすいと推定される。
 また、本開示に係る平版印刷版の製造方法において、シリケート化合物等のインヒビターを多く含まない現像液を用いるので、現像液活性の電導度管理が可能であると推察される。
 以下、本開示に係る平版印刷版原版に含まれる各構成要件の詳細について説明する。
Further, in the method of manufacturing a lithographic printing plate according to the present disclosure, since a developer containing no silicate compound is used, it is presumed that silicate residue can be easily suppressed.
Further, in the method for producing a lithographic printing plate according to the present disclosure, since a developer that does not contain a large amount of an inhibitor such as a silicate compound is used, it is presumed that the conductivity of the developer activity can be controlled.
Hereinafter, details of each constituent element included in the planographic printing plate precursor according to the present disclosure will be described.
〔画像記録層〕
 本開示に係る平版印刷版原版における画像記録層は、アルカリ可溶性樹脂、重量平均分子量4,000以上の赤外線吸収剤(特定高分子化赤外線吸収剤)、及びオニウム塩化合物を含む。
[Image recording layer]
The image recording layer in the lithographic printing plate precursor according to the present disclosure contains an alkali-soluble resin, an infrared absorber having a weight average molecular weight of 4,000 or more (specific polymerized infrared absorber), and an onium salt compound.
<アルカリ可溶性樹脂>
 本開示に係る平版印刷版原版における画像記録層は、アルカリ可溶性樹脂を含む。
 なお、本開示における「アルカリ可溶性」とは、25℃の1mol/L水酸化ナトリウム溶液に可溶であることをいう。また、「可溶である」とは、100mLの溶媒に0.1g以上溶解することをいう。
 アルカリ可溶性樹脂としては、アセタール樹脂、フェノール樹脂、アクリル樹脂、及び、ウレア結合、ウレタン結合又はアミド結合を主鎖に有する樹脂よりなる群から選ばれる少なくとも1種の樹脂を含むことが好ましい。
<Alkali-soluble resin>
The image recording layer in the lithographic printing plate precursor according to the present disclosure contains an alkali-soluble resin.
The term "alkali-soluble" 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 preferably contains at least one resin selected from the group consisting of an acetal resin, a phenol resin, an acrylic resin, and a resin having a urea bond, a urethane bond or an amide bond in its main chain.
-アセタール樹脂-
 アセタール樹脂としては、特に限定されず公知の樹脂を使用することができるが、例えば、国際公開第2014/106554号の段落0012~段落0021に記載のアセタール樹脂が挙げられる。
-Acetal resin-
The acetal resin is not particularly limited and known resins can be used, and examples thereof include the acetal resins described in paragraphs 0012 to 0021 of International Publication No. 2014/106554.
-フェノール樹脂-
 フェノール樹脂としては、重量平均分子量が2,000を超えるフェノール樹脂であることが好ましい。重量平均分子量が2,000を超えるフェノール樹脂は、構造単位としてフェノール、又は、置換フェノール類を含むフェノール樹脂であり、好ましくはノボラック樹脂である。
 ノボラック樹脂は、平版印刷版原版において、未露光部において強い水素結合性を生起し、露光部において一部の水素結合が容易に解除されるといった点から、本開示における画像記録層に好ましく用いられるアルカリ可溶性樹脂である。
 このノボラック樹脂は、分子内に構造単位としてフェノール類を含むものであれば特に制限はない。
 本開示におけるノボラック樹脂は、フェノール、以下に示される置換フェノール類と、アルデヒド類との縮合反応により得られる樹脂であり、フェノール類としては、具体的には、フェノール、イソプロピルフェノール、t-ブチルフェノール、t-アミルフェノール、ヘキシルフェノール、シクロヘキシルフェノール、3-メチル-4-クロロ-6-t-ブチルフェノール、イソプロピルクレゾール、t-ブチルクレゾール、t-アミルクレゾールが挙げられる。好ましくは、t-ブチルフェノール、t-ブチルクレゾールである。
 また、アルデヒド類の例としては、ホルムアルデヒド、アセトアルデヒド、アクロレイン、クロトンアルデヒド等の脂肪族及び芳香族アルデヒドが挙げられる。好ましくは、ホルムアルデヒド、アセトアルデヒドである。
 より具体的には、本開示におけるノボラック樹脂しては、例えば、フェノールとホルムアルデヒドとの縮重合体(フェノールホルムアルデヒド樹脂)、m-クレゾールとホルムアルデヒドとの縮重合体(m-クレゾールホルムアルデヒド樹脂)、p-クレゾールとホルムアルデヒドとの縮重合体(p-クレゾールホルムアルデヒド樹脂)、m-/p-混合クレゾールとホルムアルデヒドとの縮重合体(m-/p-混合クレゾールホルムアルデヒド樹脂)、フェノールとクレゾール(m-,p-,又はm-/p-混合のいずれでもよい)とホルムアルデヒドとの縮重合体(フェノール/クレゾール(m-,p-,又はm-/p-混合のいずれでもよい)混合ホルムアルデヒド樹脂)等が挙げられる。
 また、ノボラック樹脂としては、更に、米国特許第4,123,279号明細書に記載されているように、t-ブチルフェノールホルムアルデヒド樹脂、オクチルフェノールホルムアルデヒド樹脂のような、炭素数3~8のアルキル基を置換基として有するフェノールとホルムアルデヒドとの縮重合体が挙げられる。
 これらノボラック樹脂の中でも、特に好ましいものとして、フェノールホルムアルデヒド樹脂、フェノール/クレゾール混合ホルムアルデヒド樹脂が挙げられる。
-Phenolic resin-
The phenol resin 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, and is preferably a novolak 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. Specific examples of the phenol include phenol, isopropylphenol, t-butylphenol, Examples thereof include t-amylphenol, hexylphenol, cyclohexylphenol, 3-methyl-4-chloro-6-t-butylphenol, isopropylcresol, t-butylcresol and t-amylcresol. Preferred are t-butylphenol and t-butylcresol.
In addition, examples of aldehydes include aliphatic and aromatic aldehydes such as formaldehyde, acetaldehyde, acrolein, and crotonaldehyde. Formaldehyde and acetaldehyde are preferable.
More specifically, 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. Is mentioned.
Further, as the 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.
 また、上記のフェノール樹脂は、レゾール樹脂であることが好ましい。レゾール樹脂としては、既述のフェノール類とアルデヒド類とを塩基性条件下で縮合させて得られる樹脂が挙げられる。
 また、レゾール樹脂は、目的に応じて、フェノール類とホルムアルデヒドとの縮合の程度、分子量、残存モノマーの残留率等は、適宜設定することができる。
Further, the above-mentioned phenol resin is preferably a resol resin. Examples of the resole resin include resins obtained by condensing the above-mentioned phenols and aldehydes under basic conditions.
The degree of condensation of phenols and formaldehyde, the molecular weight, the residual monomer residual ratio, etc. of the resole resin can be appropriately set according to the purpose.
 好ましいレゾール樹脂としては、例えば、フェノールとホルムアルデヒドから得られるレゾール樹脂、m-クレゾールとホルムアルデヒドから得られるレゾール樹脂、p-クレゾールとホルムアルデヒドから得られるレゾール樹脂、o-クレゾールとホルムアルデヒドから得られるレゾール樹脂、ビスフェノールAとホルムアルデヒドから得られるレゾール樹脂、4,4’―ビスフェノールAとホルムアルデヒドから得られるレゾール樹脂等が挙げられる。 Preferred resole resins include, for example, resole resins obtained from phenol and formaldehyde, resole resins obtained from m-cresol and formaldehyde, resole resins obtained from p-cresol and formaldehyde, resole resins obtained from o-cresol and formaldehyde, Examples thereof include a resole resin obtained from bisphenol A and formaldehyde, a resole resin obtained from 4,4′-bisphenol A and formaldehyde, and the like.
 レゾール樹脂としては、市販品を用いてもよい。市販品としては、具体的には、例えば住友ベークライト株式会社製のスミライトレジンPR-9480、同PR-14170、同PR-51107、同EM-1、同PR-EPN、同PR-UFC-504(いずれも商品名)、Lekai社製のR-32等(製品名)を用いることができる。
 また、特公平6-50394号公報に記載のレゾール樹脂を用いることができる。
A commercial item may be used as the resol resin. Examples of commercially available products are, for example, Sumirite Resin PR-9480, PR-14170, PR-51107, EM-1, PR-EPN, and PR-UFC-504 manufactured by Sumitomo Bakelite Co., Ltd. (Both are trade names), Lekai R-32, etc. (product name) can be used.
Further, the resole resin described in JP-B-6-50394 can be used.
 上記フェノール樹脂の重量平均分子量は、好ましくは2,000を超え50,000以下であり、2,500~20,000であることが更に好ましく、3,000~10,000であることが特に好ましい。また、分散度(重量平均分子量/数平均分子量)は、1.1~10であることが好ましい。
 上記数平均分子量は、テトラヒドロフラン(THF)を溶剤とした場合のゲルパーミエーションクロマトグラフィ(GPC)により測定されるポリスチレン換算の数平均分子量である。
 このようなフェノール樹脂は、1種のみを用いてもよく、2種以上を混合して用いてもよい。
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 (weight average molecular weight / number average molecular weight) 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.
Such phenolic resins may be used alone or in combination of two or more.
-ウレア結合、ウレタン結合又はアミド結合を主鎖に有する樹脂-
 ウレア結合、ウレタン結合又はアミド結合を主鎖に有する樹脂としては、得られる平版印刷版の耐刷性の観点から、ウレア結合、ウレタン結合及びアミド結合の少なくともいずれか1つの結合を主鎖に有することが好ましく、ウレア結合、アミド結合のいずれか1つの結合を主鎖に有することがより好ましく、ウレア結合を主鎖に有することが更に好ましい。また、上記樹脂としては、ポリウレア樹脂、ポリウレタン樹脂、ポリアミド樹脂等が挙げられる。
 ウレア結合、ウレタン結合又はアミド結合を主鎖に有する樹脂としては、従来公知のものであれば特に制限はないが、例えば、国際公開第2015/152209号のポリウレア樹脂、ポリウレタン樹脂が好ましく使用される。
 このようなウレア結合、ウレタン結合又はアミド結合を主鎖に有する樹脂は、1種のみを用いてもよく、2種以上を混合して用いてもよい。
-A resin having a urea bond, a urethane bond or an amide bond in the main chain-
The resin having a urea bond, urethane bond or amide bond in the main chain has at least one bond of urea bond, urethane bond and amide bond in the main chain from the viewpoint of printing durability of the lithographic printing plate obtained. It is preferable that the main chain has any one of a urea bond and an amide bond, and it is further preferable that the main chain has a urea bond. Examples of the resin include polyurea resin, polyurethane resin, polyamide resin and the like.
The resin having a urea bond, urethane bond or amide bond in the main chain is not particularly limited as long as it is a conventionally known one, but for example, polyurea resin and polyurethane resin of WO 2015/152209 are preferably used. .
As the resin having a urea bond, urethane bond or amide bond in the main chain, only one kind may be used, or two or more kinds may be mixed and used.
-アクリル樹脂-
 アクリル樹脂としては、ポジ型平版印刷版原版の画像記録層に用いるものとして公知のものを特に制限なく使用することができる。
 アクリル樹脂は1種のみを用いてもよく、2種以上を混合して用いてもよい。
 アクリル樹脂としては、(メタ)アクリル化合物により形成される構成単位の含有量が50質量%以上である樹脂が好ましい。
 上記(メタ)アクリル化合物としては、アクリル酸メチル、アクリル酸エチル、アクリル酸プロピル、アクリル酸ベンジル、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸シクロヘキシル、メタクリル酸ベンジル、等のアルキルアクリレートやアルキルメタクリレート。2-ヒドロキシエチルアクリレート又は2-ヒドロキシエチルメタクリレート等の脂肪族水酸基を有するアクリル酸エステル類、及びメタクリル酸エステル類。
 アクリルアミド、メタクリルアミド、N-メチルアクリルアミド、N-エチルアクリルアミド、N-フェニルアクリルアミド、等のアクリルアミド若しくはメタクリルアミド。ビニルアセテート、ビニルクロロアセテート、ビニルブチレート、安息香酸ビニル等のビニルエステル類。
 スチレン、α-メチルスチレン、メチルスチレン、クロロメチルスチレン等のスチレン類。
 N-ビニルピロリドン、N-ビニルピリジン、アクリロニトリル、メタクリロニトリル等のその他の窒素原子含有モノマー。
 N-メチルマレイミド、N-エチルマレイミド、N-プロピルマレイミド、N-ブチルマレイミド、N-フェニルマレイミド、N-2-メチルフェニルマレイミド、N-2,6-ジエチルフェニルマレイミド、N-2-クロロフェニルマレイミド、N-シクロヘキシルマレイミド、N-ラウリルマレイミド、N-ヒドロキシフェニルマレイミド、等のマレイミド類が挙げられる。
-acrylic resin-
As the acrylic resin, those known as those used for the image recording layer of the positive type lithographic printing plate precursor can be used without particular limitation.
The acrylic resin may be used alone or in combination of two or more.
The acrylic resin is preferably a resin in which the content of the constituent unit formed by the (meth) acrylic compound is 50% by mass or more.
Examples of the (meth) acrylic compound include alkyl acrylates and alkyl methacrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, benzyl acrylate, methyl methacrylate, ethyl methacrylate, cyclohexyl methacrylate and benzyl methacrylate. Acrylic acid esters and methacrylic acid esters having an aliphatic hydroxyl group such as 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate.
Acrylamide or methacrylamide such as acrylamide, methacrylamide, N-methyl acrylamide, N-ethyl acrylamide, N-phenyl acrylamide. Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate.
Styrenes such as styrene, α-methylstyrene, methylstyrene and chloromethylstyrene.
Other nitrogen atom-containing monomers such as N-vinylpyrrolidone, N-vinylpyridine, acrylonitrile and methacrylonitrile.
N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-phenylmaleimide, N-2-methylphenylmaleimide, N-2,6-diethylphenylmaleimide, N-2-chlorophenylmaleimide, Maleimides such as N-cyclohexylmaleimide, N-laurylmaleimide, N-hydroxyphenylmaleimide and the like can be mentioned.
 上記アルカリ可溶性樹脂は、現像ラチチュード及び耐キズ性の観点から、アクリル樹脂に由来する構成単位を含むことが好ましく、下記式1で表される構成単位と、側鎖にフェノール性水酸基(「フェノール性ヒドロキシ基」ともいう。)を有する構成単位と、を有することがより好ましい。
 上記アルカリ可溶性樹脂は、マレイミド化合物と(メタ)アクリル化合物又はスチレン化合物とを少なくとも共重合してなる共重合体であることが好ましく、マレイミド化合物と(メタ)アクリルアミド化合物とを少なくとも共重合してなる共重合体であることがより好ましい。
From the viewpoint of development latitude and scratch resistance, the alkali-soluble resin preferably contains a structural unit derived from an acrylic resin, and a structural unit represented by the following formula 1 and a phenolic hydroxyl group (“phenolic group” in the side chain). Also referred to as a “hydroxy group”).
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 is obtained by at least copolymerizing a maleimide compound and a (meth) acrylamide compound. It is more preferably a copolymer.
-式1で表される構成単位-
 上記アルカリ可溶性樹脂は、現像ラチチュード及び耐キズ性の観点から、下記式1で表される構成単位を有することが好ましい。
 下記式1で表される構成単位は、マレイミド化合物由来の構成単位(マレイミド化合物を共重合してなる構成単位)であることが好ましい。
-Structural unit represented by Formula 1-
From the viewpoint of development latitude and scratch resistance, the alkali-soluble resin preferably has a structural unit represented by the following formula 1.
The structural unit represented by the following formula 1 is preferably a structural unit derived from a maleimide compound (a structural unit obtained by copolymerizing a maleimide compound).
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
 式1中、Rは、アルキル基又はアリール基を表す。 In Formula 1, R represents an alkyl group or an aryl group.
 式1のRにおけるアルキル基及びアリール基は、置換基を有していてもよい。
 置換基としては、アルキル基、アリール基、ハロゲン原子、ヒドロキシ基、アルコキシ基、カルボキシ基、アルコキシカルボニル基、アシル基、アシルオキシ基、シアノ基等が挙げられる。上記置換基が更に置換基を有していてもよい。
 式1のRのアルキル基の炭素原子数(「炭素数」ともいう。)は、1~20であることが好ましく、1~12であることがより好ましく、1~8であることが更に好ましい。また、式1のRのアルキル基の炭素原子数は、現像ラチチュードの観点からは、2以上であることが好ましい。
 式1のRのアリール基の炭素原子数は、6~20であることが好ましく、6~12であることがより好ましく、6~10であることが更に好ましい。
 また、式1のRのアリール基は、単環構造のアリール基であっても、2環以上が縮合した構造のアリール基であってもよい。
 式1におけるRは、耐キズ性の観点から、炭素原子数1~20のアルキル基、又は、炭素原子数6~20のアリール基であることが好ましく、炭素原子数1~12のアルキル基、又は、炭素原子数6~12のアリール基であることがより好ましく、メチル基、n-ブチル基、ベンジル基、フェニル基、又は、ナフチル基であることが更に好ましく、n-ブチル基、ベンジル基、又は、フェニル基であることが特に好ましく、フェニル基であることが最も好ましい。
 また、式1におけるRは、現像ラチチュード及び耐キズ性の観点から、アリール基であることが好ましい。
The alkyl group and aryl group for R in Formula 1 may have a substituent.
Examples of the substituent 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 Formula 1 is preferably 1 to 20, more preferably 1 to 12, and further preferably 1 to 8. . Further, the number of carbon atoms of the alkyl group represented by R in Formula 1 is preferably 2 or more from the viewpoint of development latitude.
The aryl group of R in formula 1 preferably has 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms, and further preferably 6 to 10 carbon atoms.
Further, the aryl group represented by R in 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.
From the viewpoint of scratch resistance, R in Formula 1 is preferably an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and an alkyl group having 1 to 12 carbon atoms, Or, an aryl group having 6 to 12 carbon atoms is more preferable, a methyl group, an n-butyl group, a benzyl group, a phenyl group, or a naphthyl group is further preferable, and an n-butyl group, a benzyl group. , Or a phenyl group is particularly preferable, and a phenyl group is most preferable.
Further, R in Formula 1 is preferably an aryl group from the viewpoint of development latitude and scratch resistance.
 式1のRにおけるアルキル基として、具体的には、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、s-ブチル基、t-ブチル基、シクロヘキシル基、ベンジル基等が挙げられる。
 式1のRにおけるアリール基として、具体的には、フェニル基、ナフチル基等が挙げられる。
Specific examples of the alkyl group represented by R in Formula 1 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. To be
Specific examples of the aryl group represented by R in Formula 1 include a phenyl group and a naphthyl group.
 式1で表される構成単位を形成するモノマーとしては、N-メチルマレイミド、N-n-ブチルマレイミド、N-ベンジルマレイミド、N-フェニルマレイミド、N-ナフチルマレイミド等が挙げられるが、本開示はこれらに限定されるものではない。 Examples of the monomer forming the constitutional unit represented by Formula 1 include N-methylmaleimide, Nn-butylmaleimide, N-benzylmaleimide, N-phenylmaleimide, N-naphthylmaleimide, etc. It is not limited to these.
 式1で表される構成単位の具体例としては、以下に示すものが好ましく挙げられる。 As specific examples of the constitutional unit represented by the formula 1, those shown below are preferably mentioned.
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
 上記アルカリ可溶性樹脂は、上記式1で表される構成単位を、1種単独で有していても、2種以上を有していてもよい。
 上記式1で表される構成単位の含有量(2種以上である場合には総含有量。以下同じ。)は、現像ラチチュード及び耐キズ性の観点から、上記アルカリ可溶性樹脂の全量に対し、10モル%~80モル%であることが好ましく、10モル%~60モル%であることがより好ましく、20モル%~55モル%であることが特に好ましい。
 なお、本開示において、「構成単位」の含有量をモル比で規定する場合、上記「構成単位」は「モノマー単位」と同義であるものとする。また、本開示において上記「モノマー単位」は、高分子反応等により重合後に修飾されていてもよい。以下においても同様である。
The alkali-soluble resin may have one kind of the structural unit represented by the above formula 1 or two or more kinds.
From the viewpoint of development latitude and scratch resistance, the content of the constitutional unit represented by the above formula 1 (total content in the case of two or more kinds, the same applies below) is based on the total amount 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%.
In the present disclosure, when the content of the “constituent unit” is defined by the molar ratio, the “constituent unit” is synonymous with the “monomer unit”. Further, in the present disclosure, the “monomer unit” may be modified after polymerization by a polymer reaction or the like. The same applies to the following.
-側鎖にフェノール性水酸基を有する構成単位-
 上記アルカリ可溶性樹脂は、側鎖にフェノール性水酸基を有する構成単位を有することが好ましい。
 上記側鎖にフェノール性水酸基を有する構成単位が有するフェノール性水酸基の数は、特に制限はないが、現像性及び現像ラチチュードの観点から、1個~4個であることが好ましく、1個又は2個であることがより好ましく、1個であることが特に好ましい。
-Structural unit having a phenolic hydroxyl group on the side chain-
The alkali-soluble resin preferably has a structural unit having a phenolic hydroxyl group on its side 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.
 上記側鎖にフェノール性水酸基を有する構成単位におけるフェノール性水酸基を有する構造としては、現像ラチチュード及び耐キズ性の観点から、窒素原子を有することが好ましく、下記式(Ph-1)で表される構造であることがより好ましい。 The structure having a phenolic hydroxyl group in the constituent unit having a phenolic hydroxyl group in the side chain preferably has a nitrogen atom from the viewpoint of development latitude and scratch resistance, and is represented by the following formula (Ph-1). The structure is more preferable.
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
 式(Ph-1)中、Rph1はそれぞれ独立に、一価の置換基を表し、Rph2は、水素原子、アルキル基又はアリール基を表し、n1は1~4の整数を表し、n2は0~4の整数を表し、波線部分は他の構造との結合位置を表す。 Wherein (Ph-1), 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, and the wavy line represents the bonding position with another structure.
 式(Ph-1)におけるRph1はそれぞれ独立に、アルキル基、アリール基、ハロゲン原子、アルコキシ基、カルボキシ基、アルコキシカルボニル基、アシル基、アシルオキシ基、シアノ基、又は、スルホンアミド基であることが好ましく、アルキル基、アリール基、ハロゲン原子、又は、スルホンアミド基であることがより好ましい。
 式(Ph-1)におけるRph2は、現像ラチチュード及び耐キズ性の観点から、水素原子又はアルキル基であることが好ましく、水素原子であることがより好ましい。
 式(Ph-1)におけるn1は、現像性及び現像ラチチュードの観点から、1又は2であることが好ましく、1であることがより好ましい。
 また、式(Ph-1)におけるフェノール性水酸基の結合位置は、特に制限はないが、現像性及び現像ラチチュードの観点から、式(Ph-1)における窒素原子の結合位置に対し、オルト位(o位)又はパラ位(p位)であることが好ましく、パラ位であることがより好ましい。
 式(Ph-1)におけるn2は、0~2の整数であることが好ましく、0又は1であることがより好ましく、0であることが特に好ましい。
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.
From the viewpoint of development latitude and scratch resistance, R ph2 in formula (Ph-1) is preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom.
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.
 また、上記側鎖にフェノール性水酸基を有する構成単位は、現像ラチチュード及び耐キズ性の観点から、アミド結合を有することが好ましく、下記式(Ph-2)で表される構成単位であることがより好ましい。 Further, the structural unit having a phenolic hydroxyl group in the side chain preferably has an amide bond from the viewpoint of development latitude and scratch resistance, and is a structural unit represented by the following formula (Ph-2). More preferable.
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
 式(Ph-2)中、Rph1はそれぞれ独立に、一価の置換基を表し、Rph2は、水素原子、アルキル基又はアリール基を表し、Rph3は、水素原子又はメチル基を表し、n1は1~4の整数を表し、n2は0~4の整数を表す。 Wherein (Ph-2), 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, and n2 represents an integer of 0 to 4.
 式(Ph-2)におけるRph1、Rph2、n1及びn2はそれぞれ、式(Ph-1)におけるRph1、Rph2、n1及びn2と同義であり、好ましい態様も同様である。
 式(Ph-2)におけるRph3は、水素原子であることが好ましい。
Each 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.
 上記側鎖にフェノール性水酸基を有する構成単位を形成するモノマーとしては、フェノール性水酸基を有するアクリルアミド、メタクリルアミド、アクリル酸エステル、メタクリル酸エステル、又は、ヒドロキシスチレン等が挙げられる。具体的にはN-(2-ヒドロキシフェニル)アクリルアミド、N-(3-ヒドロキシフェニル)アクリルアミド、N-(4-ヒドロキシフェニル)アクリルアミド、N-(2-ヒドロキシフェニル)メタクリルアミド、N-(3-ヒドロキシフェニル)メタクリルアミド、N-(4-ヒドロキシフェニル)メタクリルアミド、o-ヒドロキシフェニルアクリレート、m-ヒドロキシフェニルアクリレート、p-ヒドロキシフェニルアクリレート、o-ヒドロキシフェニルメタクリレート、m-ヒドロキシフェニルメタクリレート、p-ヒドロキシフェニルメタクリレート、o-ヒドロキシスチレン、m-ヒドロキシスチレン、p-ヒドロキシスチレン、2-(2-ヒドロキシフェニル)エチルアクリレート、2-(3-ヒドロキシフェニル)エチルアクリレート、2-(4-ヒドロキシフェニル)エチルアクリレート、2-(2-ヒドロキシフェニル)エチルメタクリレート、2-(3-ヒドロキシフェニル)エチルメタクリレート、2-(4-ヒドロキシフェニル)エチルメタクリレート等を好適に使用することができる。 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. Specifically, N- (2-hydroxyphenyl) acrylamide, N- (3-hydroxyphenyl) acrylamide, N- (4-hydroxyphenyl) acrylamide, N- (2-hydroxyphenyl) methacrylamide, N- (3- Hydroxyphenyl) methacrylamide, N- (4-hydroxyphenyl) methacrylamide, o-hydroxyphenyl acrylate, m-hydroxyphenyl acrylate, p-hydroxyphenyl acrylate, o-hydroxyphenyl methacrylate, m-hydroxyphenyl methacrylate, p-hydroxy Phenyl methacrylate, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, 2- (2-hydroxyphenyl) ethyl acrylate, 2- (3-hydroxyphenyl) Preferable are tyl acrylate, 2- (4-hydroxyphenyl) ethyl acrylate, 2- (2-hydroxyphenyl) ethyl methacrylate, 2- (3-hydroxyphenyl) ethyl methacrylate, 2- (4-hydroxyphenyl) ethyl methacrylate and the like. Can be used.
 上記側鎖にフェノール性水酸基を有する構成単位の具体例としては、下記に示すものが好ましく挙げられる。 Specific examples of the structural unit having a phenolic hydroxyl group in the above side chain are preferably those shown below.
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
 上記アルカリ可溶性樹脂は、上記側鎖にフェノール性水酸基を有する構成単位を、1種単独で有していても、2種以上を有していてもよい。
 上記側鎖にフェノール性水酸基を有する構成単位の含有量は、現像ラチチュード及び耐キズ性の観点から、上記アルカリ可溶性樹脂の全量に対し、10モル%~80モル%であることが好ましく、10モル%~60モル%であることがより好ましく、20モル%~55モル%であることが特に好ましい。
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.
From the viewpoint of development latitude and scratch resistance, the content of the structural 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, and 10 mol%. % To 60 mol% is more preferable, and 20 mol% to 55 mol% is particularly preferable.
 また、上記アルカリ可溶性樹脂における上記式1で表される構成単位と上記側鎖にフェノール性水酸基を有する構成単位とのモル比は、特に制限はないが、現像ラチチュード及び耐キズ性の観点から、上記式1で表される構成単位:上記側鎖にフェノール性水酸基を有する構成単位=2:1~1:2であることが好ましく、1.5:1~1:1.5であることがより好ましく、1.2:1~1:1.2であることが特に好ましい。 The molar ratio of the structural unit represented by Formula 1 and the structural unit having a phenolic hydroxyl group on the side chain in the alkali-soluble resin is not particularly limited, but from the viewpoint of development latitude and scratch resistance, Structural unit represented by the above formula 1: structural unit having a phenolic hydroxyl group on the side chain = 2: 1 to 1: 2 is preferable, and 1.5: 1 to 1: 1.5 is preferable. More preferably, 1.2: 1 to 1: 1.2 is particularly preferable.
-シアノ基を有する構成単位-
 上記アルカリ可溶性樹脂は、現像ラチチュード及び耐キズ性の観点から、シアノ基を有する構成単位を更に有することが好ましい。
 上記シアノ基を有する構成単位としては、現像ラチチュード及び耐キズ性の観点から、下記式(2-1)で表される構成単位であることが好ましく、下記式(2-2)で表される構成単位であることがより好ましい。
-Structural unit having a cyano group-
From the viewpoint of development latitude and scratch resistance, it is preferable that the alkali-soluble resin further has a constitutional unit having a cyano group.
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 scratch resistance, and is represented by the following formula (2-2). It is more preferably a structural unit.
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
 式(2-1)中、RCNは、水素原子又はメチル基を表し、XCNは、単結合又は-(YCNnCN-ZCN-を表し、YCNは、-CONH-又は-COO-を表し、nCNは、0又は1を表し、ZCNはアルキレン基、アリーレン基、又は、アルキレン基、アリーレン基及びエーテル結合よりなる群から選ばれた少なくとも2以上の基を結合した基を表す。 In formula (2-1), R CN represents a hydrogen atom or a methyl group, X CN represents a single bond or — (Y CN ) nCN —Z CN —, and Y CN represents —CONH— or —COO. Represents —, nCN represents 0 or 1, and 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. .
 式(2-1)におけるRCNは、水素原子であることが好ましい。
 式(2-1)におけるXCNは、単結合であることが好ましい。
 式(2-1)におけるYCNは、-CONH-であることが好ましい。
 式(2-1)におけるnCNは、1であることが好ましい。
 式(2-1)のZCNにおけるアルキレン基としては、炭素原子数2~6のアルキレン基が好ましく、炭素原子数2~6の直鎖アルキレン基がより好ましい。
 式(2-1)のZCNにおけるアリーレン基としては、フェニレン基又はナフチレン基が好ましく、フェニレン基がより好ましい。
 式(2-1)におけるZCNは、アルキレン基、アリーレン基、又は、アリーレン基-O-アルキレン基であることが好ましく、アルキレン基、又は、アリーレン基であることがより好ましい。
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.
 上記シアノ基を有する構成単位を形成するモノマーの具体例としては、アクリロニトリル、メタクリロニトリル、2-シアノエチルアクリレート、2-シアノエチルメタクリレート、2-シアノエチルアクリルアミド、2-シアノエチルメタクリルアミド、p-シアノフェニルメタクリルアミド、p-シアノフェニルメタクリレート、p-シアノフェニルアクリルアミド、p-シアノフェニルアクリレート、o-シアノフェニルメタクリルアミド、o-シアノフェニルメタクリレート、o-シアノフェニルアクリルアミド、o-シアノフェニルアクリレート、p-(2-シアノエチルオキシ)フェニルメタクリルアミド、p-(2-シアノエチルオキシ)フェニルメタクリレート、o-(2-シアノエチルオキシ)フェニルメタクリルアミド、o-(2-シアノエチルオキシ)フェニルメタクリレート、p-(2-シアノエチルオキシ)フェニルアクリルアミド、p-(2-シアノエチルオキシ)フェニルアクリレート、o-(2-シアノエチルオキシ)フェニルアクリルアミド、o-(2-シアノエチルオキシ)フェニルアクリレートなどが挙げられるが、本開示はこれらに限定されるものではない。
 これらの中でも、アクリロニトリル、アクリルアミド化合物、又は、メタクリルアミド化合物が、耐薬品性が良好であり好ましい。更に、その中でも、アクリロニトリル、N-フェニルアクリルアミド化合物、又は、N-フェニルメタクリルアミド化合物が特に好ましい。
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. , P-cyanophenyl methacrylate, p-cyanophenyl acrylamide, p-cyanophenyl acrylate, o-cyanophenyl methacrylamide, o-cyanophenyl methacrylate, o-cyanophenyl acrylamide, o-cyanophenyl acrylate, p- (2-cyanoethyl) (Oxy) phenylmethacrylamide, p- (2-cyanoethyloxy) phenylmethacrylate, o- (2-cyanoethyloxy) phenylmethacrylamide o- (2-cyanoethyloxy) phenyl methacrylate, p- (2-cyanoethyloxy) phenylacrylamide, p- (2-cyanoethyloxy) phenyl acrylate, o- (2-cyanoethyloxy) phenylacrylamide, o- (2-cyanoethyl (Oxy) phenyl acrylate and the like, but the present disclosure is not limited thereto.
Among these, 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.
 上記アルカリ可溶性樹脂は、上記シアノ基を有する構成単位を、1種単独で有していても、2種以上を有していてもよい。
 上記アルカリ可溶性樹脂が上記シアノ基を有する構成単位を有する場合、上記シアノ基を有する構成単位の含有量は、現像ラチチュード及び耐キズ性の観点から、上記アルカリ可溶性樹脂の全量に対し、1モル%~50モル%であることが好ましく、5モル%~40モル%であることがより好ましく、10モル%~30モル%であることが特に好ましい。
The alkali-soluble resin may have one type of structural unit having a cyano group, or may have two or more types.
When the alkali-soluble resin has a structural unit having the cyano group, the content of the structural unit having the cyano group is 1 mol% based on the total amount of the alkali-soluble resin from the viewpoint of development latitude and scratch resistance. It is preferably ˜50 mol%, more preferably 5 mol% to 40 mol%, and particularly preferably 10 mol% to 30 mol%.
-カルボキシ基を有する構成単位-
 上記アルカリ可溶性樹脂は、現像性、現像ラチチュード及び耐キズ性の観点から、カルボキシ基を有する構成単位を更に有することが好ましい。
 上記カルボキシ基を有する構成単位としては、現像性、現像ラチチュード及び耐キズ性の観点から、下記式(Ac)で表される構成単位であることが好ましい。
-Structural unit having a carboxy group-
From the viewpoint of developability, development latitude and scratch resistance, 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 viewpoint of developability, development latitude and scratch resistance.
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
 式(Ac)中、RAcは、水素原子又はメチル基を表す。 In formula (Ac), R Ac represents a hydrogen atom or a methyl group.
 式(Ac)におけるRAcは、水素原子であることが好ましい。
 上記カルボキシ基を有する構成単位を形成するモノマーの具体例としては、アクリル酸、メタクリル酸、無水マレイン酸、イタコン酸等、カルボキシ基とエチレン性不飽和基とを分子内にそれぞれ1以上有する不飽和カルボン酸が挙げられる。
 中でも、アクリル酸又はメタクリル酸が好ましく、アクリル酸がより好ましい。
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.
 上記アルカリ可溶性樹脂は、上記カルボキシ基を有する構成単位を、1種単独で有していても、2種以上を有していてもよい。
 上記アルカリ可溶性樹脂が上記カルボキシ基を有する構成単位を有する場合、上記カルボキシ基を有する構成単位の含有量は、現像ラチチュード及び耐キズ性の観点から、上記アルカリ可溶性樹脂の全量に対し、1モル%~50モル%であることが好ましく、2モル%~40モル%であることがより好ましく、5モル%~30モル%であることが特に好ましい。
The alkali-soluble resin may have one kind of the structural unit having a carboxy group, or may have two or more kinds.
When the alkali-soluble resin has a structural unit having a carboxy group, the content of the structural unit having a carboxy group is 1 mol% with respect to the total amount of the alkali-soluble resin from the viewpoint of development latitude and scratch resistance. It is preferably from 50 to 50 mol%, more preferably from 2 to 40 mol%, particularly preferably from 5 to 30 mol%.
-その他の構成単位-
 上記アルカリ可溶性樹脂は、上述した以外のその他の構成単位を有していてもよい。
 その他の構成単位としては、特に制限はないが、アルキル(メタ)アクリレート化合物由来の構成単位(アルキル(メタ)アクリレート化合物を共重合してなる構成単位)を含むことが好ましい。
-Other building units-
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).
 上記その他の構成単位を形成するモノマーの具体例としては、下記(m1)~(m9)のモノマーが好ましく挙げられる。
 (m1)2-ヒドロキシエチルアクリレート又は2-ヒドロキシエチルメタクリレート等の脂肪族水酸基を有するアクリル酸エステル類、及びメタクリル酸エステル類。
 (m2)アクリル酸メチル、アクリル酸エチル、アクリル酸プロピル、アクリル酸ブチル、アクリル酸アミル、アクリル酸ヘキシル、アクリル酸オクチル、アクリル酸ベンジル、アクリル酸-2-クロロエチル、グリシジルアクリレート等のアルキルアクリレート。
 (m3)メタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸ブチル、メタクリル酸アミル、メタクリル酸ヘキシル、メタクリル酸シクロヘキシル、メタクリル酸ベンジル、メタクリル酸-2-クロロエチル、グリシジルメタクリレート等のアルキルメタクリレート。
 (m4)アクリルアミド、メタクリルアミド、N-メチロールアクリルアミド、N-エチルアクリルアミド、N-ヘキシルメタクリルアミド、N-シクロヘキシルアクリルアミド、N-ヒドロキシエチルアクリルアミド、N-フェニルアクリルアミド、N-ニトロフェニルアクリルアミド、N-エチル-N-フェニルアクリルアミド等のアクリルアミド若しくはメタクリルアミド、N-ビニルピロリドン。
 (m5)エチルビニルエーテル、2-クロロエチルビニルエーテル、ヒドロキシエチルビニルエーテル、プロピルビニルエーテル、ブチルビニルエーテル、オクチルビニルエーテル、フェニルビニルエーテル等のビニルエーテル類。
 (m6)ビニルアセテート、ビニルクロロアセテート、ビニルブチレート、安息香酸ビニル等のビニルエステル類。
 (m7)スチレン、α-メチルスチレン、メチルスチレン、クロロメチルスチレン等のスチレン類。
 (m8)メチルビニルケトン、エチルビニルケトン、プロピルビニルケトン、フェニルビニルケトン等のビニルケトン類。
 (m9)エチレン、プロピレン、イソブチレン、ブタジエン、イソプレン等のオレフィン類。
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.
(M3) 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.
(M7) Styrenes such as styrene, α-methylstyrene, methylstyrene and chloromethylstyrene.
(M8) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.
(M9) Olefins such as ethylene, propylene, isobutylene, butadiene and isoprene.
 上記アルカリ可溶性樹脂は、上記その他の構成単位を、1種単独で有していても、2種以上を有していてもよい。
 上記アルカリ可溶性樹脂が上記その他の構成単位を有する場合、上記その他の構成単位の含有量は、現像ラチチュード及び耐キズ性の観点から、上記アルカリ可溶性樹脂の全量に対し、1モル%~50モル%であることが好ましく、2モル%~40モル%であることがより好ましく、5モル%~30モル%であることが特に好ましい。
The alkali-soluble resin may have one of the above-mentioned other structural units alone, or may have two or more thereof.
When the alkali-soluble resin has the other structural unit, the content of the other structural unit is 1 mol% to 50 mol% based on the total amount of the alkali-soluble resin from the viewpoint of development latitude and scratch resistance. Is preferable, 2 mol% to 40 mol% is more preferable, and 5 mol% to 30 mol% is particularly preferable.
 上記アルカリ可溶性樹脂は、重量平均分子量(Mw)が2,000以上、数平均分子量が500以上のものが好ましく、重量平均分子量が5,000~300,000であり、かつ数平均分子量が800~250,000であることがより好ましい。
 また、上記アルカリ可溶性樹脂の分散度(重量平均分子量/数平均分子量)は、1.1~10であることが好ましい。
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.
The degree of dispersion (weight average molecular weight / number average molecular weight) of the alkali-soluble resin is preferably 1.1 to 10.
 上記アルカリ可溶性樹脂は、1種単独で使用しても、2種以上を併用してもよい。
 上記アルカリ可溶性樹脂の含有量は、耐刷性の観点から、画像記録層の全質量に対して、1質量%~90質量%が好ましく、3質量%~70質量%がより好ましく、5質量%~50質量%が特に好ましい。
 また、上記画像形成層が、上層及び下層を有する重層構造である場合、上記アルカリ可溶性樹脂は、下層に少なくとも含有されることが好ましい。下層における上記アルカリ可溶性樹脂の含有量としては、下層の全質量に対し、3質量%以上であることが好ましく、10質量%以上であることがより好ましく、25質量%以上であることが更に好ましい。
The above alkali-soluble resins may be used alone or in combination of two or more.
From the viewpoint of printing durability, 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.
In addition, when the image forming layer has a multilayer structure having an upper layer and a lower layer, it is preferable that 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. .
<重量平均分子量4,000以上の赤外線吸収剤>
 上記画像形成層は、重量平均分子量4,000以上の赤外線吸収剤(特定高分子化赤外線吸収剤)を含有する。
 特定高分子化赤外線吸収剤としては、重量平均分子量4,000以上であり、赤外光を吸収し熱を発生する顔料又は染料であれば特に制限はなく、赤外線吸収剤として知られる種々の顔料又は染料を用いることができる。
 現像ラチチュード及び耐キズ性の観点から、特定高分子化赤外線吸収剤の重量平均分子量としては、4,000以上50,000以下であることが好ましく、6,000以上30,000以下であることがより好ましく、7,000以上20,000以下であることが更に好ましく、8,000以上10,000以下であることが特に好ましい。
<Infrared absorber having a weight average molecular weight of 4,000 or more>
The image forming layer contains an infrared absorbing agent (specific polymerized infrared absorbing agent) having a weight average molecular weight of 4,000 or more.
The specific polymerized infrared absorber is not particularly limited as long as it is a pigment or dye having a weight average molecular weight of 4,000 or more and absorbing infrared light to generate heat, and various pigments known as infrared absorbers. Alternatively, a dye can be used.
From the viewpoint of development latitude and scratch resistance, the weight average molecular weight of the specific polymerized infrared absorber is preferably 4,000 or more and 50,000 or less, and 6,000 or more and 30,000 or less. More preferably, it is 7,000 or more and 20,000 or less, still more preferably 8,000 or more and 10,000 or less.
 特定高分子化赤外線吸収剤は、現像ラチチュードの観点から、酸性基を有することが好ましく、後述のポリマー構造が酸性基を有することがより好ましく、後述のポリマー構造がフェノール構造を有することが更に好ましい。
 酸性基としては、フェノール性水酸基、スルホンアミド基、活性イミド基等が挙げられる。これらの中でも、現像ラチチュードの観点から、酸性基としては、フェノール性水酸基又はスルホンアミド基であることが好ましい。
From the viewpoint of development latitude, the specific polymerized infrared absorber preferably has an acidic group, more preferably the polymer structure described below has an acidic group, and further preferably the polymer structure described below has a phenol structure. .
Examples of the acidic group include a phenolic hydroxyl group, a sulfonamide group and an active imide group. Among these, from the viewpoint of development latitude, the acidic group is preferably a phenolic hydroxyl group or a sulfonamide group.
 特定高分子化赤外線吸収剤は、赤外線を吸収する色素構造とポリマー構造とを有することが好ましい。
 特定高分子化赤外線吸収剤における赤外線を吸収する色素構造としては、公知公用の顔料及び染料が有する色素構造が挙げられる。
 具体的には、アゾ色素構造、金属錯塩アゾ色素構造、ピラゾロンアゾ色素構造、アントラキノン色素構造、フタロシアニン色素構造、カルボニウム色素構造、キノンイミン色素構造、メチン色素構造、シアニン色素構造、オキソノール色素構造などの色素構造が挙げられる。
 これらの色素構造としては、シアニン色素構造、フタロシアニン色素構造、オキソノール色素構造、スクアリリウム色素構造、ピリリウム塩色素構造、チオピリリウム色素構造及びニッケルチオレート錯体色素構造よりなる群より選ばれる少なくとも1種の色素構造が好ましく、より好ましくはシアニン色素構造が挙げられる。
The specific polymerized infrared absorber preferably has a dye structure that absorbs infrared light and a polymer structure.
Examples of the dye structure that absorbs infrared rays in the specific polymerized infrared absorber include the dye structures of known and commonly used pigments and dyes.
Specifically, dyes such as azo dye structure, metal complex azo dye structure, pyrazolone azo dye structure, anthraquinone dye structure, phthalocyanine dye structure, carbonium dye structure, quinoneimine dye structure, methine dye structure, cyanine dye structure, and oxonol dye structure. The structure is mentioned.
As these dye structures, at least one dye structure selected from the group consisting of a cyanine dye structure, a phthalocyanine dye structure, an oxonol dye structure, a squarylium dye structure, a pyrylium salt dye structure, a thiopyrylium dye structure and a nickel thiolate complex dye structure. Is more preferable, and a cyanine dye structure is more preferable.
 特定高分子化赤外線吸収剤における赤外線を吸収する色素構造を有する化合物として、中国特許出願公開第101770167号明細書の段落0016~0022に記載のシアニン染料、ハロゲン原子を有するルテニウム染料等を用いてもよい。特定高分子化赤外線吸収剤において、ハロゲン原子を有するルテニウム染料を用いた場合、特定高分子化赤外線吸収剤が含むポリマー構造部分(例えば、アルカリ可溶性樹脂のポリマー主鎖)にルテニウム染料が選択的に結合され、ルテニウム染料中のハロゲン原子が脱ハロゲン化水素反応を促進すると考えられる。 As the compound having a dye structure that absorbs infrared rays in the specific polymerized infrared absorber, a cyanine dye, a ruthenium dye having a halogen atom, etc. described in paragraphs 0016 to 0022 of Chinese Patent Application Publication No. 101770167 may be used. Good. When a ruthenium dye having a halogen atom is used in the specific polymerized infrared absorber, the ruthenium dye is selectively added to the polymer structure part (for example, the polymer main chain of the alkali-soluble resin) included in the specific polymerized infrared absorber. It is believed that the halogen atoms in the ruthenium dye that are bound together promote the dehydrohalogenation reaction.
 特定高分子化赤外線吸収剤におけるポリマー構造としては、既述のアルカリ可溶性樹脂が有するポリマー構造が挙げられる。特定高分子化赤外線吸収剤におけるポリマー構造を形成するアルカリ可溶性樹脂としては、酸性基を有するアルカリ可溶性樹脂であることが好ましい。なお、酸性基としては、既述の酸性基と同義であり、好ましい態様も同様である。
 特定高分子化赤外線吸収剤が酸性基を有することで、酸性基と後述のオニウム塩化合物とが相互作用し、露光部の溶解性を小さくし、また、非露光部は現像液に対する溶解性が高まり、現像ラチチュードが向上するものと推察される。
 上記観点から、アルカリ可溶性樹脂としては、フェノール樹脂であることがより好ましく、レゾール樹脂であることが更に好ましい。
 上記フェノール樹脂及びレゾール樹脂は、既述のフェノール樹脂の具体例と同義であり、好ましい態様も同様である。
Examples of the polymer structure of the specific polymerized infrared absorber include the polymer structure of the alkali-soluble resin described above. The alkali-soluble resin forming the polymer structure in the specific polymerized infrared absorber is preferably an alkali-soluble resin having an acidic group. The acidic group has the same meaning as the acidic group described above, and the preferred embodiments are also the same.
Since the specific polymerized infrared absorber has an acidic group, the acidic group interacts with an onium salt compound described below to reduce the solubility of the exposed area, and the unexposed area has a low solubility in a developing solution. It is presumed that the development latitude increases and the development latitude improves.
From the above viewpoint, the alkali-soluble resin is more preferably a phenol resin, further preferably a resol resin.
The above-mentioned phenol resin and resol resin have the same meanings as the specific examples of the phenol resin described above, and the preferred embodiments are also the same.
 また、グラフト重合反応の行いやすさから、特定高分子化赤外線吸収剤におけるアルカリ可溶性樹脂は、下記式S-1で表される構成単位を有することが好ましい。
 特定高分子化赤外線吸収剤におけるアルカリ可溶性樹脂は、アルカリ可溶性樹脂を構成する全構成単位において、下記式S-1で表される構成単位を2種以上含んでいてもよい。
In addition, the alkali-soluble resin in the specific polymerized infrared absorbing agent preferably has a structural unit represented by the following formula S-1 from the viewpoint of easy graft polymerization reaction.
The alkali-soluble resin in the specific polymerized infrared absorber may include two or more kinds of structural units represented by the following formula S-1 in all structural units constituting the alkali-soluble resin.
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
 式S-1中、RS1は、それぞれ独立に、メチロール(CHOH)基、又は、下記式S-2で表される基を表し、RS2は、それぞれ独立に、アルキル基、又はハロゲン原子を表し、p1は、1~3の整数を表し、p2は0~2の整数を表し、波線部分は他の構造との結合位置を表す。 In formula S-1, R S1's each independently represent a methylol (CH 2 OH) group or a group represented by the following formula S-2, and R S2's each independently represent an alkyl group or halogen. Represents an atom, p1 represents an integer of 1 to 3, p2 represents an integer of 0 to 2, and a wavy line portion represents a bonding position with another structure.
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
 式S-2中、Lは単結合、又は、アルキレン基を表し、RS3は、それぞれ独立に、アルキル基、又は、メチロール基を表し、p3は0~2の整数を表し、波線部分は式S-1中のRS1との結合部位を表す。
 式S-2中、Lとしては、炭素数1~10のアルキレン基が好ましく、炭素数1~5のアルキレン基であることがより好ましく、炭素数1~4のアルキレン基であることが更に好ましい。
 式S-2中、RS3は、炭素数1~4のアルキル基、又は、メチロール基であることが好ましく、より好ましくはメチロール基である。
 式S-2中、p3としては、1又は2であることが好ましく、より好ましくは2である。
 式S-2中、フェニル基におけるOH基の位置は、式S-1中のRS1との結合部位に対して、オルト位及びパラ位よりなる群から選ばれた少なくとも1つの位置に有することが好ましく、パラ位に少なくとも有することがより好ましい。
In formula S-2, L s represents a single bond or an alkylene group, R S3 each independently represents an alkyl group or a methylol group, p3 represents an integer of 0 to 2, and the wavy line portion represents Represents a binding site with R S1 in formula S-1.
In formula S-2, L s is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, and further preferably an alkylene group having 1 to 4 carbon atoms. preferable.
In formula S-2, R S3 is preferably an alkyl group having 1 to 4 carbon atoms or a methylol group, and more preferably a methylol group.
In Formula S-2, p3 is preferably 1 or 2, and more preferably 2.
In formula S-2, the position of the OH group in the phenyl group must be at least one position selected from the group consisting of ortho and para positions with respect to the binding site with R S1 in formula S-1. Is preferred, and it is more preferred to have at least the para position.
 式S-1におけるRS2は、炭素数1~6アルキル基であることが好ましく、炭素数1~4のアルキル基であることがより好ましく、炭素数1又は2のアルキル基であることがより好ましい。
 式S-1におけるRS1は、メチロール基又は式S-2で表される基であることが好ましい。式S-1におけるRS1が式S-2で表される基である場合、式S-2中、Lは炭素数1~10のアルキレン基(より好ましくは、炭素数1~5のアルキレン基であり、更に好ましくは炭素数1~4のアルキレン基である)であり、RS3は、炭素数1~4のアルキル基又はメチロール基(より好ましくはメチロール基である)であり、p3としては、1又は2(より好ましくは2である)であることが好ましい。
 式S-1におけるp2は、0又は1であることが好ましい。
 式S-1におけるp1は、1又は2であることが好ましい。
 式S-1におけるp1は、1であり、p2が1であることが好ましい。
R S2 in the formula S-1 is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and further preferably an alkyl group having 1 or 2 carbon atoms. preferable.
R S1 in formula S-1 is preferably a methylol group or a group represented by formula S-2. When R S1 in the formula S-1 is a group represented by the formula S-2, in the formula S-2, L s is an alkylene group having 1 to 10 carbon atoms (more preferably an alkylene group having 1 to 5 carbon atoms). A group, more preferably an alkylene group having 1 to 4 carbon atoms), R S3 is an alkyl group having 1 to 4 carbon atoms or a methylol group (more preferably a methylol group), and as p3 Is preferably 1 or 2 (more preferably 2).
P2 in formula S-1 is preferably 0 or 1.
It is preferable that p1 in the formula S-1 is 1 or 2.
In formula S-1, p1 is preferably 1 and p2 is preferably 1.
 特定高分子化赤外線吸収剤におけるアルカリ可溶性樹脂が有する構成単位の具体例を下記に示すが、本開示における特定高分子化赤外線吸収剤におけるアルカリ可溶性樹脂が有する構成単位は、これに限定されるものではない。 Specific examples of the constituent units contained in the alkali-soluble resin in the specific polymerized infrared absorbent are shown below, but the constituent units contained in the alkali-soluble resin in the specific polymerized infrared absorbent in the present disclosure are not limited thereto. is not.
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
 上記構造式I-1又はI-2中、n11及びn12は、それぞれ独立に、1~12の整数を表し、*は、赤外線を吸収する色素構造又は他の構成単位との結合部分を表す。 In the above structural formula I-1 or I-2, n11 and n12 each independently represent an integer of 1 to 12, and * represents a dye structure that absorbs infrared rays or a bonding portion with another structural unit.
 特定高分子化赤外線吸収剤において、ポリマー構造と赤外線を吸収する色素構造とは、エーテル結合を介して形成されていることが好ましい。
 現像ラチチュード及び耐キズ性の観点から、特定高分子化赤外線吸収剤は、上記構造I-1又は構造I-2と、後述のシアニン染料と、がエーテル結合を介して形成された化合物であることが好ましい。
 また、特定高分子化赤外線吸収剤において色素構造は、ポリマー構造の側鎖に有することが好ましい。
In the specific polymerized infrared absorber, the polymer structure and the infrared absorbing dye structure are preferably formed through an ether bond.
From the viewpoint of development latitude and scratch resistance, the specific polymerized infrared absorber is a compound in which the above structure I-1 or structure I-2 and a cyanine dye described later are formed through an ether bond. Is preferred.
In the specific polymerized infrared absorber, the dye structure preferably has a side chain of the polymer structure.
 特定高分子化赤外線吸収剤の具体例としては、例えば、フェノール樹脂とシアニン色素とが結合された化合物等が挙げられる。 Specific examples of the specific polymerized infrared absorber include, for example, a compound in which a phenol resin and a cyanine dye are bonded.
 特定高分子化赤外線吸収剤に対する赤外線を吸収する色素構造部分の含有量としては、14質量%~75質量%であることが好ましく、より好ましくは、25質量%~65質量%である。特定高分子化赤外線吸収剤に対する赤外線を吸収する色素構造部分の含有量が、14質量%以上であると、現像ラチチュード及び耐傷性により優れる。また、上記赤外線を吸収する色素構造部分の含有量が75質量%以下であると、特定高分子化赤外線吸収剤のアルカリ可溶性に優れるので、現像液中の現像カス抑制性により優れる。 The content of the dye structure portion that absorbs infrared rays with respect to the specific polymerized infrared absorber is preferably 14% by mass to 75% by mass, and more preferably 25% by mass to 65% by mass. When the content of the dye structure portion that absorbs infrared rays with respect to the specific polymerized infrared absorber is 14% by mass or more, the development latitude and scratch resistance are more excellent. Further, when the content of the dye structure portion that absorbs infrared rays is 75% by mass or less, the specific polymerized infrared absorbing agent is excellent in alkali solubility, and thus the development dregs suppressing property in the developing solution is more excellent.
 上記特定高分子化赤外線吸収剤は、1種単独で使用しても、2種以上を併用してもよい。
 上記画像形成層における特定高分子化赤外線吸収剤(他の赤外線吸収剤を含む場合には、合計量)の含有量としては、感度、画像形成層の均一性及び、耐久性の観点から、上記画像形成層の全質量に対し、0.01質量%~50質量%であることが好ましく、0.1質量%~30質量%であることがより好ましく、1.0質量%~30質量%であることが特に好ましい。
The specific polymerized infrared absorbers may be used alone or in combination of two or more.
The content of the specific polymerized infrared absorber (in the case of containing other infrared absorbers, the total amount) in the image forming layer, from the viewpoint of sensitivity, uniformity of the image forming layer, and durability, It is preferably 0.01% by mass to 50% by mass, more preferably 0.1% by mass to 30% by mass, and 1.0% by mass to 30% by mass with respect to the total mass of the image forming layer. It is particularly preferable that
 また、画像記録層において、特定高分子化赤外線吸収剤と、ポリマー構造を有さない赤外線吸収剤(以下、単に「他の赤外線吸収剤」ともいう。)と、を併用してもよい。 Further, in the image recording layer, the specific polymerized infrared absorber and the infrared absorber having no polymer structure (hereinafter, also simply referred to as “other infrared absorber”) may be used in combination.
 他の赤外線吸収剤における顔料としては、市販の顔料、並びに、カラーインデックス(C.I.)便覧、「最新顔料便覧」(日本顔料技術協会編、1977年刊)、「最新顔料応用技術」(CMC出版、1986年刊)及び「印刷インキ技術」CMC出版、1984年刊)に記載されている顔料を利用することができる。 As pigments in other infrared absorbers, commercially available pigments, color index (CI) handbook, "latest pigment handbook" (edited by Japan Pigment Technology Association, published in 1977), "latest pigment application technology" (CMC) Published in 1986) and "Printing Ink Technology" published by CMC, published in 1984).
 顔料の種類としては、例えば、黒色顔料、黄色顔料、オレンジ色顔料、褐色顔料、赤色顔料、紫色顔料、青色顔料、緑色顔料、蛍光顔料、金属粉顔料、ポリマー結合色素が挙げられる。具体的には、不溶性アゾ顔料、アゾレーキ顔料、縮合アゾ顔料、キレートアゾ顔料、フタロシアニン系顔料、アントラキノン系顔料、ペリレン及びペリノン系顔料、チオインジゴ系顔料、キナクリドン系顔料、ジオキサジン系顔料、イソインドリノン系顔料、キノフタロン系顔料、染付けレーキ顔料、アジン顔料、ニトロソ顔料、ニトロ顔料、天然顔料、蛍光顔料、無機顔料、カーボンブラックを用いることができる。
 顔料は表面処理をせずに用いてもよく、従来公知の表面処理を施して用いてもよい。
 顔料の粒径は、0.01μm~10μmが好ましく、0.05μm~1μmがより好ましく、0.1μm~1μmが更に好ましい。上記範囲であると、顔料の分散物の感熱層塗布液中での安定性、感熱層の均一性等の点で好ましい。
 顔料を分散する方法としては、例えば、「最新顔料応用技術」(CMC出版、1986年刊)等に記載されているインキ製造やトナー製造等に用いられる公知の分散技術が使用できる。
Examples of types of pigments 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. Specifically, insoluble azo pigments, azo lake pigments, condensed azo pigments, chelate azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments. 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 μm to 10 μm, more preferably 0.05 μm to 1 μm, and further preferably 0.1 μm to 1 μm. Within the above range, the stability of the pigment dispersion in the heat-sensitive layer coating solution, the uniformity of the heat-sensitive layer, and the like are preferable.
As 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.
 他の赤外線吸収剤としては、染料が好ましく挙げられる。
 本開示において用いることができる他の赤外線吸収剤としては、市販の染料及び文献(例えば「染料便覧」有機合成化学協会編集、昭和45年刊)に記載されている公知のものが利用できる。具体的には、アゾ染料、金属錯塩アゾ染料、ピラゾロンアゾ染料、アントラキノン染料、フタロシアニン染料、カルボニウム染料、キノンイミン染料、メチン染料、シアニン染料、オキソノール染料などの染料が挙げられる。
 具体的には、例えば、特開平7-285275号公報の段落0020~0021に記載されている化合物、及び、「エレクトロニクス関連色素-現状と将来展望-」第16章(株)シーエムシー(1998年刊)等の公知資料に記載されている化合物が挙げられる。
 本開示において、これらの染料のうち、赤外光又は近赤外光を少なくとも吸収するものが、赤外光又は近赤外光を発光するレーザーでの利用に適する点で好ましく、シアニン染料が特に好ましい。
As another infrared absorber, a dye is preferably mentioned.
As other infrared absorbers that can be used in the present disclosure, commercially available dyes and known ones described in the 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.
Specifically, for example, the compounds described in paragraphs 0020 to 0021 of JP-A-7-285275, and "Electronics-related dyes-present state and future prospect-", Chapter 16 CMC (published in 1998) ) And the like described in publicly known materials.
In the present disclosure, among 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.
 そのような赤外光又は近赤外光を少なくとも吸収する染料としては、例えば、特開昭58-125246号、特開昭59-84356号、特開昭59-202829号、特開昭60-78787号等の各公報に記載されているシアニン染料、特開昭58-173696号、特開昭58-181690号、特開昭58-194595号等の各公報に記載されているメチン染料、特開昭58-112793号、特開昭58-224793号、特開昭59-48187号、特開昭59-73996号、特開昭60-52940号、特開昭60-63744号等の各公報に記載されているナフトキノン染料、特開昭58-112792号公報等に記載されているスクワリリウム色素、英国特許434,875号明細書及びに記載のシアニン染料等を挙げることができる。
 また、染料として米国特許第5,156,938号明細書記載の近赤外吸収増感剤も好適に用いられ、また、米国特許第3,881,924号明細書記載の置換されたアリールベンゾ(チオ)ピリリウム塩、特開昭57-142645号公報(米国特許第4,327,169号明細書)記載のトリメチンチアピリリウム塩、特開昭58-181051号、同58-220143号、同59-41363号、同59-84248号、同59-84249号、同59-146063号、同59-146061号の各公報に記載されているピリリウム系化合物、特開昭59-216146号公報記載のシアニン色素、米国特許第4,283,475号明細書に記載のペンタメチンチオピリリウム塩等や特公平5-13514号、同5-19702号公報に開示されているピリリウム化合物等が、市販品としては、エポリン社製のEpolight III-178、Epolight III-130、Epolight III-125等が特に好ましく用いられる。
 また、染料として特に好ましい別の例として米国特許第4,756,993号明細書中に式(I)、(II)として記載されている近赤外吸収染料を挙げることができる。
Examples of 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. Naphthoquinone dyes described in JP-A-58-112792, squarylium dyes described in JP-A-58-112792, and cyanine dyes described in British Patent 434,875 and the like. Rukoto can.
Further, a near infrared absorption sensitizer described in US Pat. No. 5,156,938 is also preferably used as a dye, and a substituted arylbenzo described in US Pat. No. 3,881,924 is also used. (Thio) pyrylium salt, the trimethine thiapyrylium salt described in JP-A-57-142645 (US Pat. No. 4,327,169), JP-A-58-181051, JP-A-58-220143, and JP-A-58-220143. 59-41363, 59-84248, 59-84249, 59-146063, 59-146061 and pyrylium compounds described in JP-A-59-216146. Cyanine dyes, pentamethine thiopyrylium salts described in U.S. Pat. No. 4,283,475, and Japanese Patent Publication Nos. 5-13514 and 5-19702. Pyrylium compounds disclosed in distribution is, as commercially available products, Epolight III-178 of Eporin Co., Epolight III-130, Epolight III-125 and the like are particularly preferably used.
Another particularly preferable example of the dye is a near-infrared absorbing dye described as formulas (I) and (II) in US Pat. No. 4,756,993.
 これらの染料のうち特に好ましいものとしては、シアニン色素、フタロシアニン染料、オキソノール染料、スクアリリウム色素、ピリリウム塩、チオピリリウム染料、ニッケルチオレート錯体が挙げられる。更に、下記式(a)で表されるシアニン色素は、本開示における上層に使用した場合に、高い重合活性を与え、かつ、安定性、経済性に優れるため最も好ましい。 Particularly preferred among these dyes are cyanine dyes, phthalocyanine dyes, oxonol dyes, squarylium dyes, pyrylium salts, thiopyrylium dyes, and nickel thiolate complexes. Furthermore, the cyanine dye represented by the following formula (a) is most preferable because it gives a high polymerization activity when used in the upper layer of the present disclosure and is excellent in stability and economy.
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
 式(a)中、Xは、水素原子、ハロゲン原子、ジアリールアミノ基(-NPh)、X-L又は以下に示す基を表し、Xは、酸素原子又は硫黄原子を表し、Lは、炭素数1~12の炭化水素基、ヘテロ原子を有する芳香族環、又はヘテロ原子を含む炭素数1~12の炭化水素基を表す。なお、ここでヘテロ原子とは、N、S、O、ハロゲン原子、及び、Seを表す。 In the formula (a), X 1 represents a hydrogen atom, a halogen atom, a diarylamino group (-NPh 2 ), X 2 -L 1 or a group shown below, X 2 represents an oxygen atom or a sulfur atom, L 1 represents a hydrocarbon group having 1 to 12 carbon atoms, an aromatic ring having a hetero atom, or a hydrocarbon group having 1 to 12 carbon atoms containing a hetero atom. In addition, a hetero atom here represents N, S, O, a halogen atom, and Se.
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
 上記式中、Xa-は後述するZa-と同様に定義され、Raは、水素原子、アルキル基、アリール基、置換又は無置換のアミノ基、及び、ハロゲン原子よりなる群から選択される置換基を表す。 In the above formula, Xa is defined in the same manner as Za described later, and R a 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.
 R21及びR22は、それぞれ独立に、炭素数1~12の炭化水素基を示す。画像記録層塗布液の保存安定性から、R21及びR22は、炭素数2個以上の炭化水素基であることが好ましく、更に、R21とR22とは互いに結合し、5員環又は6員環を形成していることが特に好ましい。 R 21 and R 22 each independently 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及びArは、それぞれ同じでも異なっていてもよく、置換基を有していてもよい芳香族炭化水素基を示す。好ましい芳香族炭化水素基としては、ベンゼン環及びナフタレン環が挙げられる。また、好ましい置換基としては、炭素数12個以下の炭化水素基、ハロゲン原子、炭素数12個以下のアルコキシ基が挙げられる。
 Y11及びY12は、それぞれ同じでも異なっていてもよく、硫黄原子又は炭素数12個以下のジアルキルメチレン基を示す。R23及びR24は、それぞれ同じでも異なっていてもよく、置換基を有していてもよい炭素数20個以下の炭化水素基を示す。好ましい置換基としては、炭素数12個以下のアルコキシ基、カルボキシ基、又は、スルホ基が挙げられる。
 R25、R26、R27及びR28は、それぞれ同じでも異なっていてもよく、水素原子又は炭素数12個以下の炭化水素基を示す。原料の入手性から、好ましくは水素原子である。また、Zaは、対アニオンを示す。但し、式(a)で示されるシアニン色素がその構造内にアニオン性の置換基を有し、電荷の中和が必要ない場合は、Zaは必要ない。好ましいZaは、画像記録層塗布液の保存安定性から、ハロゲン化物イオン、過塩素酸イオン、テトラフルオロボレートイオン、ヘキサフルオロホスフェートイオン、及びスルホン酸イオンであり、特に好ましくは、過塩素酸イオン、ヘキサフルオロホスフェートイオン、及びアリールスルホン酸イオンである。
Ar 1 and Ar 2 may be the same or different and each represents an aromatic hydrocarbon group which may have a substituent. Preferred aromatic hydrocarbon groups include a benzene ring and a naphthalene ring. 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.
Y 11 and Y 12, which may be the same or different, each represents a sulfur atom or a dialkylmethylene group having 12 or less carbon atoms. R 23 and R 24, which may be the same or different, each represents a hydrocarbon group having 20 or less carbon atoms, which may have a substituent. Preferred substituents include an alkoxy group having 12 or less carbon atoms, a carboxy group, or a sulfo group.
R 25 , R 26 , R 27 and R 28, which may be the same or different, each represents a hydrogen atom or a hydrocarbon group having 12 or less carbon atoms. From the availability of raw materials, hydrogen atom is preferable. 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. , Hexafluorophosphate ion, and arylsulfonate ion.
 好適に用いることのできる式(a)で示されるシアニン色素の具体例としては、特開2001-133969号公報の段落0017~0019、特開2002-40638号公報の段落0012~0038、特開2002-23360号公報の段落0012~0023に記載されたものを挙げることができる。
 他の赤外線吸収剤として特に好ましくは、以下に示すシアニン染料Aである。
Specific examples of the 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.
Particularly preferable as the other infrared absorbing agent is the cyanine dye A shown below.
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
 上記他の赤外線吸収剤は、1種単独で使用しても、2種以上を併用してもよい。
 その他の赤外線吸収剤の含有量としては、上記特定高分子化赤外線吸収剤の含有量よりも少ないことが好ましい。
 また、上記画像形成層が、上層及び下層を有する重層構造である場合、上記特定高分子化赤外線吸収剤は上層及び/又は下層に含有することができる。上層と下層の赤外線吸収剤は同じ上記特定高分子化赤外線吸収剤であっても、異なる赤外線吸収剤との併用であってもよく、上記特定高分子化赤外線吸収剤が上層にあることがより好ましい。
 また、特定高分子化赤外線吸収剤及び他の赤外線吸収剤を併用する場合、特定高分子化赤外線吸収剤及び他の赤外線吸収剤の含有量比としては、質量基準で9:1~1:9が好ましく、より好ましくは、8:2~2:8である。
The other infrared absorbers may be used alone or in combination of two or more.
The content of the other infrared absorbing agent is preferably smaller than the content of the specific polymerized infrared absorbing agent.
When the image forming layer has a multilayer structure having an upper layer and a lower layer, the specific polymerized infrared absorber can be contained in the upper layer and / or the lower layer. The infrared absorbers of the upper layer and the lower layer may be the same specific polymerized infrared absorber as described above, or may be used in combination with different infrared absorbents, and the specific polymerized infrared absorber may be present in the upper layer. preferable.
When the specific polymerized infrared absorber and the other infrared absorber are used in combination, the content ratio of the specific polymerized infrared absorber and the other infrared absorber is 9: 1 to 1: 9 on a mass basis. Is preferable, and more preferably 8: 2 to 2: 8.
<オニウム塩化合物>
 本開示に係る平版印刷版原版は、オニウム塩化合物を含有する。
 現像ラチチュード及び耐キズ性の観点から、オニウム塩化合物としては、スルホニウム塩及化合物及び第4級アンモニウム塩化合物よりなる群から選ばれる少なくとも1種の化合物であることが好ましく、スルホニウム塩化合物であることがより好ましい。
 オニウム塩化合物は、1種単独で使用しても、2種以上を併用してもよい。
<Onium salt compound>
The lithographic printing plate precursor according to the present disclosure contains an onium salt compound.
From the viewpoint of development latitude and scratch resistance, the onium salt compound is preferably at least one compound selected from the group consisting of sulfonium salts and quaternary ammonium salt compounds, and is preferably a sulfonium salt compound. Is more preferable.
The onium salt compounds may be used alone or in combination of two or more.
-スルホニウム塩化合物-
 スルホニウム塩化合物としては、下記式(S)で表されるスルホニウム塩であることが好ましい。
-Sulfonium salt compound-
The sulfonium salt compound is preferably a sulfonium salt represented by the following formula (S).
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
 式(S)中、R~Rはそれぞれ独立に、炭素原子数20以下のアルキル基又は炭素原子数20以下のアリール基を表し、Xは、スルホン酸イオン、カルボン酸イオン、ハロゲン原子を有する無機酸イオン又はハロゲン化物イオンを表す。 In 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, and X is a sulfonate ion, a carboxylate ion, or a halogen atom. Represents an inorganic acid ion or a halide ion having.
 式(S)におけるR~Rはそれぞれ独立に、炭素原子数20以下のアルキル基又は炭素原子数20以下のアリール基であり、互いに結合して環を形成することはない。
 式(S)のR~Rにおけるアルキル基及びアリール基は、置換基を有していてもよい。好ましい置換基としては、ハロゲン原子、ニトロ基、炭素原子数12以下のアルキル基、炭素原子数12以下のアルコキシ基、又は、炭素原子数12以下のアリールオキシ基が挙げられる。中でも、現像ラチチュード及び耐キズ性の観点から、ハロゲン原子又はニトロ基が好ましく、ハロゲン原子がより好ましく、塩素原子が特に好ましい。
 式(S)におけるR~Rはそれぞれ独立に、現像ラチチュード及び耐キズ性の観点から、炭素原子数1以上20以下のアルキル基又は炭素原子数6以上20以下のアリール基であることが好ましく、炭素原子数6以上20以下のアリール基であることがより好ましい。
 上記アルキル基としては、直鎖状であっても、分岐を有していても、環構造を有していてもよく、炭素原子数1~8のアルキル基であることが好ましく、炭素原子数1~4のアルキル基であることがより好ましく、メチル基であることが特に好ましい。
 また、上記アリール基としては、現像ラチチュード及び耐キズ性の観点から、1以上のハロゲン原子を有するアリール基であることが好ましく、1以上のハロゲン原子を有するフェニル基であることがより好ましく、1以上の塩素原子(クロロ基)を有するフェニル基であることが特に好ましい。
 また、上記フェニル基におけるハロゲン原子を有する位置は、オルト位及びパラ位よりなる群から選ばれた少なくとも1つの位置に有することが好ましく、パラ位に少なくとも有することがより好ましい。
 式(S)で表されるスルホニウム塩化合物は、現像ラチチュード及び耐キズ性の観点から、トリアリールスルホニウム塩化合物であることが好ましく、硫黄原子に結合しているアリール基の芳香環がハロゲン原子を化合物全体として1以上有するトリアリールスルホニウム塩化合物であることがより好ましく、硫黄原子に結合している3つの各アリール基の芳香環がハロゲン原子をそれぞれ1以上有するトリアリールスルホニウム塩化合物であることが更に好ましく、硫黄原子に結合している3つの各アリール基の芳香環が塩素原子をそれぞれ1以上有するトリアリールスルホニウム塩化合物であることが特に好ましい。
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. Among them, a halogen atom or a nitro group is preferable, a halogen atom is more preferable, and a chlorine atom is particularly preferable, from the viewpoint of development latitude and scratch resistance.
In the formula (S), R 1 to R 3 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 scratch resistance. An aryl group having 6 to 20 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. It is more preferably 1 to 4 alkyl groups, and particularly preferably a methyl group.
In addition, 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 scratch resistance. A phenyl group having the above chlorine atom (chloro group) is particularly preferable.
In addition, 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 scratch resistance, and the aromatic ring of the aryl group bonded to the sulfur atom has a halogen atom. The compound as a whole is more preferably a triarylsulfonium salt compound having one or more compounds, and is preferably a triarylsulfonium salt compound having an aromatic ring of each of the three aryl groups bonded to a sulfur atom having one or more halogen atoms. More preferably, it is a triarylsulfonium salt compound in which the aromatic ring of each of the three aryl groups bonded to the sulfur atom has at least one chlorine atom.
 式(S)におけるXは、現像ラチチュード及び耐キズ性の観点から、スルホン酸イオン、ハロゲン原子を有する無機酸イオン又はハロゲン化物イオンであることが好ましく、スルホン酸イオンであることがより好ましい。
 また、式(S)におけるXは、現像ラチチュード及び耐キズ性の観点から、芳香族基を有することが好ましい。
 更に、式(S)におけるXは、現像ラチチュード及び耐キズ性の観点から、フェノール性水酸基を有することが好ましい。
 また更に、式(S)におけるXは、現像ラチチュード及び耐キズ性の観点から、ジアリールケトン構造を有することが好ましい。
 中でも、式(S)におけるXは、現像ラチチュード及び耐キズ性の観点から、フェノール性水酸基及びジアリールケトン構造を有することが特に好ましい。
From the viewpoint of development latitude and scratch resistance, 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.
Further, X in the formula (S) preferably has an aromatic group from the viewpoint of development latitude and scratch resistance.
Further, X in the formula (S) preferably has a phenolic hydroxyl group from the viewpoint of development latitude and scratch resistance.
Further, X in the formula (S) preferably has a diarylketone structure from the viewpoint of development latitude and scratch resistance.
Among them, it is particularly preferable that X in the formula (S) has a phenolic hydroxyl group and a diarylketone structure from the viewpoint of development latitude and scratch resistance.
 また、式(S)におけるXの共役酸(XH)のpKa(酸解離定数)は、5未満であることが好ましく、-10以上5未満であることがより好ましく、-10以上2以下であることが特に好ましい。
 なお、本開示におけるpKaは、水中のpKaであり、Advanced Chemistry Development社製ACD/Labs software Ver 8.0 for Microsoft windowsのACD/pKa DB ver 8.07を使用して計算するものとする。
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.
 式(S)におけるXとして具体的には、塩化物イオン、臭化物イオン、ヨウ化物イオン、BF 、PF 、トリフルオロメタンスルホン酸イオン、p-トルエンスルホン酸イオン、メタンスルホン酸イオン、又は、下記式(X-1)で表されるアニオンであることが好ましく、下記式(X-1)で表されるアニオンであることが特に好ましい。
 なお、下記式(X-1)で表されるアニオンは、フェノール性水酸基及びジアリールケトン構造を有するアニオンである。
Specific examples of 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.
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
 上記式(S)で表されるスルホニウム塩化合物は、平版印刷版原版の白灯下での取り扱い性の観点から、極大吸収波長を波長400nm以下に有する化合物であることが好ましく、極大吸収波長を波長360nm以下に有する化合物であることがより好ましい。 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.
 上記式(S)で表されるスルホニウム塩化合物は、1種単独で用いてもよいし、2種以上を併用してもよい。
 上記式(S)で表されるスルホニウム塩化合物の含有量は、現像ラチチュード及び耐キズ性の観点から、画像記録層の全質量に対して、0.1質量%~50質量%が好ましく、0.5質量%~40質量%がより好ましく、1質量%~30質量%が特に好ましい。
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 scratch resistance. It is more preferably 0.5% by mass to 40% by mass, and particularly preferably 1% by mass to 30% by mass.
-第4級アンモニウム塩化合物-
 第4級アンモニウム塩化合物としては第4級アンモニウム塩化合物における第4級アンモニウムカチオンは、一価のカチオンであっても、第4級アンモニウム構造を2以上有する二価以上のカチオンであってもよいが、一価のカチオンであることが好ましい。
 上記第4級アンモニウム塩化合物における対アニオンは、電荷を中和できるアニオンであれば、一価のアニオンであっても、二価以上のアニオンであってもよいが、一価のアニオンであることが好ましい。
-Quaternary ammonium salt compound-
As the quaternary ammonium salt compound, the quaternary ammonium cation in the quaternary ammonium salt compound may be a monovalent cation or a divalent or higher cation having two or more quaternary ammonium structures. Is preferably a monovalent cation.
The counter anion in the quaternary ammonium salt compound may be a monovalent anion or a divalent or higher valent anion as long as it is an anion capable of neutralizing the charge, but it is a monovalent anion. Is preferred.
 上記第4級アンモニウム塩化合物における第4級アンモニウムカチオンは、下記式(Am-1)で表されるカチオンであることが好ましく、下記式(Am-2)で表されるカチオンであることがより好ましく、下記式(Am-3)で表されるカチオンであることが特に好ましい。 The quaternary ammonium cation in the above quaternary ammonium salt compound is preferably a cation represented by the following formula (Am-1), and more preferably a cation represented by the following formula (Am-2). A cation represented by the following formula (Am-3) is particularly preferable.
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
 式(Am-1)中、Rm1~Rm4はそれぞれ独立に、炭素原子を1個以上含む置換基を表し、また、Rm1~Rm4のうちの2つ以上が互いに結合して環構造を形成してもよい。
 式(Am-2)中、C~Cは炭素原子を表し、Nは窒素原子を表し、R~R17はそれぞれ独立に、水素原子又は置換基を表し、Lは、CとCとを連結する単結合又は二重結合、又は、-C-C-N-C-C-を含む環構造を形成する2価の連結基を表し、m1及びm2はそれぞれ独立に、0~5の整数を表し、n1及びn2はそれぞれ独立に、0又は正の整数を表す。
In formula (Am-1), R m1 to R m4 each independently represent a substituent containing at least one carbon atom, and two or more of R m1 to R m4 are bonded to each other to form a ring structure. May be formed.
In formula (Am-2), C 1 to C 6 represent carbon atoms, N 1 represents a nitrogen atom, R 4 to R 17 each independently represent a hydrogen atom or a substituent, and L 3 represents C 3 and C 4 and a single or double bond linking, or, -C 3 -C 1 -N 1 -C 2 -C 4 - represents a divalent linking group to form a ring structure containing, m1 and m2 each independently represents an integer of 0 to 5, and n1 and n2 each independently represent 0 or a positive integer.
 式(Am-1)におけるRm1~Rm4で表される炭素原子を1個以上含む置換基としては、以下のものを例示することができる。
 例えば、アルキル基(好ましくは炭素数1~20であり、より好ましくは炭素数1~16、特に好ましくは炭素数1~12であり、具体的には、例えばメチル基、エチル基、n-ブチル基、iso-プロピル基、tert-ブチル基、n-オクチル基、n-デシル基、n-ヘキサデシル基、シクロプロピル基、シクロペンチル基、シクロヘキシル基、2-シクロヘキシルエチル基等が挙げられる。)、アルケニル基(好ましくは炭素数2~20、より好ましくは炭素数2~12、特に好ましくは炭素数2~8であり、例えばビニル基、アリル基、2-ブテニル基、3-ペンテニル基、2-シクロヘキセニルメチル基等が挙げられる。)、アルキニル基(好ましくは炭素数2~20、より好ましくは炭素数2~12、特に好ましくは炭素数2~8であり、例えばプロパルギル基、3-ペンチニル基等が挙げられる。)、アリール基(好ましくは炭素数6~30、より好ましくは炭素数6~20、特に好ましくは炭素数6~12であり、例えばフェニル基、p-メチルフェニル基、ナフチル基、等が挙げられる。)等が挙げられる。
Examples of the substituent containing at least one carbon atom represented by R m1 to R m4 in formula (Am-1) include the followings.
For example, an alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, specifically, for example, methyl group, ethyl group, n-butyl). Group, iso-propyl group, tert-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, 2-cyclohexylethyl group, etc.), alkenyl. A group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 8 carbon atoms), for example, vinyl group, allyl group, 2-butenyl group, 3-pentenyl group, 2-cyclo A hexenylmethyl group, etc.), an alkynyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 12 carbon atoms). And examples thereof include a propargyl group and a 3-pentynyl group.), An aryl group (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, for example, Phenyl group, p-methylphenyl group, naphthyl group, etc.) and the like.
 これらの置換基は更に置換されてもよい。また、置換基が二つ以上ある場合は、同一でも異なっていてもよい。また、可能な場合には互いに連結して環を形成していてもよい。 These substituents may be further substituted. When there are two or more substituents, they may be the same or different. If possible, they may be linked to each other to form a ring.
 式(Am-1)におけるRm1~Rm4として好ましくは、アルキル基、アリール基、又はそれらを更に任意に置換した基である。また、得られる平版印刷版の耐薬品性の観点からは、Rm1~Rm4の炭素数の合計が8~80であることが好ましく、10~64であることがより好ましく、12~48であることが特に好ましい。 R m1 to R m4 in formula (Am-1) are preferably an alkyl group, an aryl group, or a group in which any of these is further substituted. From the viewpoint of chemical resistance of the lithographic printing plate obtained, the total carbon number of R m1 to R m4 is preferably 8 to 80, more preferably 10 to 64, and 12 to 48. It is particularly preferable that
 式(Am-2)のR~R17における置換基としては、以下のものを例示することができる。
 例えば、アルキル基(好ましくは炭素数1~20であり、より好ましくは炭素数1~16、特に好ましくは炭素数1~12であり、具体的には、例えばメチル基、エチル基、n-ブチル基、iso-プロピル基、tert-ブチル基、n-オクチル基、n-デシル基、n-ヘキサデシル基、シクロプロピル基、シクロペンチル基、シクロヘキシル基、2-シクロヘキシルエチル基等が挙げられる。)、アルケニル基(好ましくは炭素数2~20、より好ましくは炭素数2~12、特に好ましくは炭素数2~8であり、例えばビニル基、アリル基、2-ブテニル基、3-ペンテニル基、2-シクロヘキセニルメチル基等が挙げられる。)、アルキニル基(好ましくは炭素数2~20、より好ましくは炭素数2~12、特に好ましくは炭素数2~8であり、例えばプロパルギル基、3-ペンチニル基等が挙げられる。)、アリール基(好ましくは炭素数6~30、より好ましくは炭素数6~20、特に好ましくは炭素数6~12であり、例えばフェニル基、p-メチルフェニル基、ナフチル基、等が挙げられる。)、
Examples of the substituent in R 4 to R 17 of the formula (Am-2) include the followings.
For example, an alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, specifically, for example, methyl group, ethyl group, n-butyl). Group, iso-propyl group, tert-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, 2-cyclohexylethyl group, etc.), alkenyl. A group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 8 carbon atoms), for example, vinyl group, allyl group, 2-butenyl group, 3-pentenyl group, 2-cyclo A hexenylmethyl group, etc.), an alkynyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 12 carbon atoms). And examples thereof include a propargyl group, a 3-pentynyl group, etc.), an aryl group (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms, for example, Phenyl group, p-methylphenyl group, naphthyl group, etc.),
 アミノ基(好ましくは炭素数0~20、より好ましくは炭素数0~12、特に好ましくは炭素数0~6であり、例えばアミノ基、メチルアミノ基、ジメチルアミノ基、ジエチルアミノ基、ジフェニルアミノ基、ジベンジルアミノ基等が挙げられる。)、アルコキシ基(好ましくは炭素数1~20、より好ましくは炭素数1~12、特に好ましくは炭素数1~8であり、例えばメトキシ基、エトキシ基、ブトキシ基等が挙げられる。)、アリールオキシ基(好ましくは炭素数6~20、より好ましくは炭素数6~16、特に好ましくは炭素数6~12であり、例えばフェニルオキシ基、2-ナフチルオキシ基等が挙げられる。)、 An amino group (preferably having 0 to 20 carbon atoms, more preferably 0 to 12 carbon atoms, particularly preferably 0 to 6 carbon atoms, for example, amino group, methylamino group, dimethylamino group, diethylamino group, diphenylamino group, A dibenzylamino group, etc.), an alkoxy group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms), for example, a methoxy group, an ethoxy group, butoxy. Group, etc.), an aryloxy group (preferably having 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms), for example, a phenyloxy group, a 2-naphthyloxy group. Etc.),
 アシル基(好ましくは炭素数1~20、より好ましくは炭素数1~16、特に好ましくは炭素数1~12であり、例えばアセチル基、ベンゾイル基、ホルミル基、ピバロイル基等が挙げられる。)、アルコキシカルボニル基(好ましくは炭素数2~20、より好ましくは炭素数2~16、特に好ましくは炭素数2~12であり、例えばメトキシカルボニル基、エトキシカルボニル基等が挙げられる。)、アリールオキシカルボニル基(好ましくは炭素数7~20、より好ましくは炭素数7~16、特に好ましくは炭素数7~10であり、例えばフェニルオキシカルボニル基などが挙げられる。)、アシルオキシ基(好ましくは炭素数2~20、より好ましくは炭素数2~16、特に好ましくは炭素数2~10であり、例えばアセトキシ基、ベンゾイルオキシ基等が挙げられる。)、アシルアミノ基(好ましくは炭素数2~20、より好ましくは炭素数2~16、特に好ましくは炭素数2~10であり、例えばアセチルアミノ基、ベンゾイルアミノ基等が挙げられる。)、 Acyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include an acetyl group, a benzoyl group, a formyl group, a pivaloyl group). Alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, and examples thereof include a methoxycarbonyl group and an ethoxycarbonyl group), aryloxycarbonyl. A group (preferably having 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, particularly preferably 7 to 10 carbon atoms, and examples thereof include a phenyloxycarbonyl group); an acyloxy group (preferably having 2 carbon atoms). To 20, more preferably 2 to 16 carbon atoms, and particularly preferably 2 to 10 carbon atoms, such as an acetoxy group, And an acylamino group (preferably having a carbon number of 2 to 20, more preferably a carbon number of 2 to 16, and particularly preferably a carbon number of 2 to 10) such as an acetylamino group and a benzoylamino group. Can be mentioned.),
 アルコキシカルボニルアミノ基(好ましくは炭素数2~20、より好ましくは炭素数2~16、特に好ましくは炭素数2~12であり、例えばメトキシカルボニルアミノ基等が挙げられる。)、アリールオキシカルボニルアミノ基(好ましくは炭素数7~20、より好ましくは炭素数7~16、特に好ましくは炭素数7~12であり、例えばフェニルオキシカルボニルアミノ基等が挙げられる。)、スルホニルアミノ基(好ましくは炭素数1~20、より好ましくは炭素数1~16、特に好ましくは炭素数1~12であり、例えばメタンスルホニルアミノ基、ベンゼンスルホニルアミノ基等が挙げられる。)、スルファモイル基(好ましくは炭素数0~20、より好ましくは炭素数0~16、特に好ましくは炭素数0~12であり、例えばスルファモイル基、メチルスルファモイル基、ジメチルスルファモイル基、フェニルスルファモイル基等が挙げられる。)、 Alkoxycarbonylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, and examples thereof include a methoxycarbonylamino group) and an aryloxycarbonylamino group. (Preferably having 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, particularly preferably 7 to 12 carbon atoms, and examples thereof include a phenyloxycarbonylamino group and the like.), Sulfonylamino group (preferably having carbon number 1 to 20, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms, and examples thereof include a methanesulfonylamino group and a benzenesulfonylamino group.), A sulfamoyl group (preferably having a carbon number of 0 to 20, more preferably 0 to 16 carbon atoms, particularly preferably 0 to 12 carbon atoms, for example Rufamoiru group, methylsulfamoyl group, dimethylsulfamoyl group, and a phenylsulfamoyl group.)
 カルバモイル基(好ましくは炭素数1~20、より好ましくは炭素数1~16、特に好ましくは炭素数1~12であり、例えばカルバモイル基、メチルカルバモイル基、ジエチルカルバモイル基、フェニルカルバモイル基等が挙げられる。)、アルキルチオ基(好ましくは炭素数1~20、より好ましくは炭素数1~16、特に好ましくは炭素数1~12であり、例えばメチルチオ基、エチルチオ基等が挙げられる。)、アリールチオ基(好ましくは炭素数6~20、より好ましくは炭素数6~16、特に好ましくは炭素数6~12であり、例えばフェニルチオ基等が挙げられる。)、スルホニル基(好ましくは炭素数1~20、より好ましくは炭素数1~16、特に好ましくは炭素数1~12であり、例えばメシル基、トシル基等が挙げられる。)、スルフィニル基(好ましくは炭素数1~20、より好ましくは炭素数1~16、特に好ましくは炭素数1~12であり、例えばメタンスルフィニル基、ベンゼンスルフィニル基等が挙げられる。)、ウレイド基(好ましくは炭素数1~20、より好ましくは炭素数1~16、特に好ましくは炭素数1~12であり、例えばウレイド基、メチルウレイド基、フェニルウレイド基等が挙げられる。)、 Carbamoyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include a carbamoyl group, a methylcarbamoyl group, a diethylcarbamoyl group and a phenylcarbamoyl group. ), An alkylthio group (preferably having a carbon number of 1 to 20, more preferably a carbon number of 1 to 16, and particularly preferably a carbon number of 1 to 12, and examples thereof include a methylthio group and an ethylthio group), an arylthio group ( It preferably has 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, and particularly preferably 6 to 12 carbon atoms, and examples thereof include a phenylthio group.), A sulfonyl group (preferably 1 to 20 carbon atoms, more preferably It preferably has 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include a mesyl group and a tosyl group. ), A sulfinyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms, and examples thereof include a methanesulfinyl group and a benzenesulfinyl group). A ureido group (preferably having a carbon number of 1 to 20, more preferably a carbon number of 1 to 16 and particularly preferably a carbon number of 1 to 12, and examples thereof include a ureido group, a methylureido group, a phenylureido group, etc.),
 リン酸アミド基(好ましくは炭素数1~20、より好ましくは炭素数1~16、特に好ましくは炭素数1~12であり、例えばジエチルリン酸アミド基、フェニルリン酸アミド基等が挙げられる。)、ヒドロキシ基、メルカプト基、ハロゲン原子(例えばフッ素原子、塩素原子、臭素原子、ヨウ素原子)、シアノ基、スルホ基、カルボキシル基、ニトロ基、ヒドロキサム酸基、スルフィノ基、ヒドラジノ基、イミノ基、ヘテロ環基(好ましくは炭素数1~30、より好ましくは炭素数1~12であり、ヘテロ原子としては、例えば窒素原子、酸素原子、硫黄原子を含むものであり、具体的には、例えばイミダゾリル基、ピリジル基、キノリル基、フリル基、チエニル基、ピペリジル基、モルホリノ基、ベンゾオキサゾリル基、ベンゾイミダゾリル基、ベンゾチアゾリル基、カルバゾリル基、アゼピニル基、オキシラニル等が挙げられる。)、シリル基(好ましくは炭素数3~40、より好ましくは炭素数3~30、特に好ましくは炭素数3~24であり、例えばトリメチルシリル基、トリフェニルシリル基等が挙げられる。)等が挙げられる。 Phosphoric acid amide group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include a diethylphosphoric acid amide group and a phenylphosphoric acid amide group. ), Hydroxy group, mercapto group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, Heterocyclic group (preferably having 1 to 30 carbon atoms, more preferably having 1 to 12 carbon atoms, and the hetero atom includes, for example, a nitrogen atom, an oxygen atom and a sulfur atom, and specifically, for example, imidazolyl. Group, pyridyl group, quinolyl group, furyl group, thienyl group, piperidyl group, morpholino group, benzoxazolyl group, benzimidazole Ryl group, benzothiazolyl group, carbazolyl group, azepinyl group, oxiranyl and the like), silyl group (preferably having 3 to 40 carbon atoms, more preferably having 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms) , For example, a trimethylsilyl group, a triphenylsilyl group, etc.) and the like.
 これらの置換基は更に置換されてもよい。また、置換基が二つ以上ある場合は、同一でも異なっていてもよい。また、可能な場合には互いに連結して環を形成していてもよい。 These substituents may be further substituted. When there are two or more substituents, they may be the same or different. If possible, they may be linked to each other to form a ring.
 式(Am-2)のR~R17における置換基として好ましくは、アルキル基、アリール基、アルケニル基、アルキニル基、又は、それらを更に任意に置換した基である。 The substituent in R 4 to R 17 of formula (Am-2) is preferably an alkyl group, an aryl group, an alkenyl group, an alkynyl group, or a group in which any of these is further substituted.
 また、式(Am-2)におけるR~R17は、互いに同一でも異なっていてもよく、互いに結合し環構造を形成してもよい。R~R17は、それぞれL又はR~R17と結合し、環構造を形成してもよい。また、C炭素原子及びC炭素原子が、それぞれC炭素原子及びC炭素原子と二重結合若しくは三重結合を形成する場合、C炭素原子及びC炭素原子がLと二重結合若しくは三重結合を形成する場合、又は、LがC炭素原子とC炭素原子とを連結する二重結合を表す場合には、それに応じて、R~R11は存在しなくてもよい。 In addition, R 4 to R 17 in formula (Am-2) may be the same or different, and may combine with each other to form a ring structure. R 4 to R 17 may be bonded to L 3 or R 4 to R 17 , respectively, to form a ring structure. Also, C 3 carbon atom and C 4 carbon atoms, to form a C 1 carbon atom and C 2 carbon atoms and a double bond or triple bond, respectively, C 3 carbon atom and C 4 carbon atom and L 3 double When a bond or a triple bond is formed or when L 3 represents a double bond connecting a C 3 carbon atom and a C 4 carbon atom, R 4 to R 11 are accordingly absent. Good.
 式(Am-2)におけるm1及びm2が2以上の場合に複数存在するR14及びR17は、互いに同一でも異なっていてもよく、互いに結合して環構造を形成してもよい。
 式(Am-2)におけるn1及びn2はそれぞれ独立に、好ましくは0、1、2又は3であり、より好ましくは0、1又は2であり、特に好ましくは0又は1である。n1及びn2が、2以上である場合に複数存在することになるR12とR13、及び、R15とR16は、互いに同一でも異なっていてもよく、互いに結合して環構造を形成してもよい。
When m1 and m2 in the formula (Am-2) are 2 or more, a plurality of R 14 and R 17 may be the same or different and may be bonded to each other to form a ring structure.
N1 and n2 in formula (Am-2) are each independently preferably 0, 1, 2 or 3, more preferably 0, 1 or 2, and particularly preferably 0 or 1. When n1 and n2 are 2 or more, a plurality of R 12 and R 13 , and R 15 and R 16 may be the same or different, and are bonded to each other to form a ring structure. May be.
 式(Am-2)のLにおける2価の連結基としては、-O-、-S-、-N(RL1)-、-C(RL2)(RL3)-が好適に挙げられる。RL1~RL3としては、水素原子又はR~R17における置換基が挙げられ、これらはそれぞれR~R14のいずれかと結合して環構造を形成してもよい。C及びCとLが二重結合を形成する場合、RL1~RL3は存在しなくてもよい。 Preferable examples of the divalent linking group for L 3 in the formula (Am-2) include —O—, —S—, —N (R L1 ) —, and —C (R L2 ) (R L3 ) —. . Examples of R L1 to R L3 include a hydrogen atom or a substituent in R 4 to R 17 , which may be bonded to any of R 4 to R 14 to form a ring structure. When C 3 and C 4 and L 3 form a double bond, R L1 to R L3 may not be present.
 式(Am-2)のR~R17及びRL1~RL3において、2つの置換基が同一原子に結合している場合、その2つの置換基が互いに同一の原子又は置換基を表し、2重結合を形成してもよい(例:R=R=Oとして、カルボニル基(-CO-)を形成してもよい。)。
 また、式(Am-2)のR~R17及びRL1~RL3において、2つの置換基が隣接する2つの原子に結合している場合、その2つの置換基が互いに同一の原子又は置換基を表し、3員環を形成してもよい。(例:R=R=Oとして、エポキシ基を形成してもよい。)
In R 4 to R 17 and R L1 to R L3 of formula (Am-2), when two substituents are bonded to the same atom, the two substituents represent the same atom or substituent, A double bond may be formed (eg, R 4 ═R 5 ═O, and a carbonyl group (—CO—) may be formed).
Further, in R 4 to R 17 and R L1 to R L3 of the formula (Am-2), when two substituents are bonded to two adjacent atoms, the two substituents are the same atom or It represents a substituent and may form a three-membered ring. (Example: R 4 = R 8 = O, and an epoxy group may be formed.)
 上記第4級アンモニウム塩化合物における第4級アンモニウムカチオンは、現像ラチチュード、耐キズ性及び得られる平版印刷版の耐薬品性の観点から、芳香環を有することが好ましい。
 また、上記第4級アンモニウム塩化合物における第4級アンモニウムカチオン及び対アニオンはそれぞれ、現像ラチチュード、耐キズ性及び得られる平版印刷版の耐薬品性の観点から、芳香環を有することが好ましい。
 また、上記第4級アンモニウム塩化合物における第4級アンモニウムカチオンは、現像ラチチュード、耐キズ性及び得られる平版印刷版の耐薬品性の観点から、脂肪族環構造を有することが好ましく、窒素原子を含む脂肪族環構造を有することがより好ましい。上記脂肪族環としては、5員環~8員環であることが好ましく、5員環又は6員環であることがより好ましく、6員環であることが特に好ましい。
 更に、上記第4級アンモニウム塩化合物における第4級アンモニウムカチオンは、現像ラチチュード、耐キズ性及び得られる平版印刷版の耐薬品性の観点から、芳香環及び脂肪族環を有することが特に好ましい。
The quaternary ammonium cation in the above quaternary ammonium salt compound preferably has an aromatic ring from the viewpoint of development latitude, scratch resistance and chemical resistance of the lithographic printing plate obtained.
The quaternary ammonium cation and the counter anion in the quaternary ammonium salt compound each preferably have an aromatic ring from the viewpoint of development latitude, scratch resistance, and chemical resistance of the lithographic printing plate obtained.
Further, the quaternary ammonium cation in the quaternary ammonium salt compound preferably has an alicyclic structure from the viewpoint of development latitude, scratch resistance and chemical resistance of the resulting lithographic printing plate, and has a nitrogen atom. More preferably, it has an aliphatic ring structure containing The aliphatic ring is preferably a 5-membered ring to an 8-membered ring, more preferably a 5-membered ring or a 6-membered ring, and particularly preferably a 6-membered ring.
Further, it is particularly preferable that the quaternary ammonium cation in the quaternary ammonium salt compound has an aromatic ring and an aliphatic ring from the viewpoints of development latitude, scratch resistance and chemical resistance of the lithographic printing plate obtained.
 上記第4級アンモニウム塩化合物における対アニオンは、現像ラチチュード、耐キズ性及び得られる平版印刷版の耐薬品性の観点から、スルホン酸イオン、カルボン酸イオン、ハロゲン原子を有する無機酸イオン、又は、ハロゲン化物イオンであることが好ましく、スルホン酸イオン、ハロゲン原子を有する無機酸イオン、又は、ハロゲン化物イオンであることがより好ましく、スルホン酸イオンであることが特に好ましい。
 また、上記第4級アンモニウム塩化合物における対アニオンは、現像ラチチュード、耐キズ性及び得られる平版印刷版の耐薬品性の観点から、芳香族基を有することが好ましい。
 更に、上記第4級アンモニウム塩化合物における対アニオンは、現像ラチチュード、耐キズ性及び得られる平版印刷版の耐薬品性の観点から、フェノール性水酸基を有することが好ましい。
 また更に、上記第4級アンモニウム塩化合物における対アニオンは、現像ラチチュード、耐キズ性及び得られる平版印刷版の耐薬品性の観点から、ジアリールケトン構造を有することが好ましい。
 中でも、上記第4級アンモニウム塩化合物における対アニオンは、現像ラチチュード、耐キズ性及び得られる平版印刷版の耐薬品性の観点から、フェノール性水酸基及びジアリールケトン構造を有することが特に好ましい。
The counter anion in the quaternary ammonium salt compound, from the viewpoint of development latitude, scratch resistance and chemical resistance of the lithographic printing plate obtained, sulfonate ion, carboxylate ion, inorganic acid ion having a halogen atom, or, A halide ion is preferable, a sulfonate ion, an inorganic acid ion having a halogen atom, or a halide ion is more preferable, and a sulfonate ion is particularly preferable.
The counter anion in the quaternary ammonium salt compound preferably has an aromatic group from the viewpoint of development latitude, scratch resistance, and chemical resistance of the lithographic printing plate obtained.
Further, the counter anion in the quaternary ammonium salt compound preferably has a phenolic hydroxyl group from the viewpoint of development latitude, scratch resistance and chemical resistance of the lithographic printing plate obtained.
Further, the counter anion in the quaternary ammonium salt compound preferably has a diarylketone structure from the viewpoint of development latitude, scratch resistance and chemical resistance of the lithographic printing plate obtained.
Among them, the counter anion in the quaternary ammonium salt compound particularly preferably has a phenolic hydroxyl group and a diarylketone structure from the viewpoints of development latitude, scratch resistance, and chemical resistance of the lithographic printing plate obtained.
 また、上記第4級アンモニウム塩化合物における対アニオンの共役酸(XH)のpKa(酸解離定数)は、5未満であることが好ましく、-10以上5未満であることがより好ましく、-10以上2以下であることが特に好ましい。
 なお、本開示におけるpKaは、水中のpKaであり、Advanced Chemistry Development社製ACD/Labs software Ver 8.0 for Microsoft windowsのACD/pKa DB ver 8.07を使用して計算するものとする。
Further, the pKa (acid dissociation constant) of the conjugate acid (XH) of the counter anion in the quaternary ammonium salt compound is preferably less than 5, more preferably -10 or more and less than 5, and more preferably -10 or more. It is particularly preferably 2 or less.
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.
 上記第4級アンモニウム塩化合物における対アニオンとして具体的には、塩化物イオン、臭化物イオン、ヨウ化物イオン、BF 、PF 、トリフルオロメタンスルホン酸イオン、p-トルエンスルホン酸イオン、メタンスルホン酸イオン、又は、下記式(X-1)で表されるアニオンであることが好ましく、下記式(X-1)で表されるアニオンであることが特に好ましい。
 なお、下記式(X-1)で表されるアニオンは、フェノール性水酸基及びジアリールケトン構造を有するアニオンである。
Specific examples of the counter anion in the quaternary ammonium salt compound include chloride ion, bromide ion, iodide ion, BF 4 , PF 6 , trifluoromethanesulfonate ion, p-toluenesulfonate ion, methanesulfone. An acid ion or 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.
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
 上記第4級アンモニウム塩化合物として、具体的には下記に示す化合物が好ましく挙げられる。 As the above quaternary ammonium salt compound, specifically, the following compounds are preferably exemplified.
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
 上記第4級アンモニウム塩化合物は、1種単独で用いてもよいし、2種以上を併用してもよい。
 上記第4級アンモニウム塩化合物の含有量は、現像ラチチュード、耐キズ性及び得られる平版印刷版の耐薬品性の観点から、画像記録層の全質量に対して、0.1質量%~50質量%が好ましく、0.5質量%~40質量%がより好ましく、1質量%~30質量%が特に好ましい。
The quaternary ammonium salt compounds may be used alone or in combination of two or more.
The content of the quaternary ammonium salt compound is 0.1% by mass to 50% by mass based on the total mass of the image recording layer from the viewpoint of development latitude, scratch resistance and chemical resistance of the lithographic printing plate obtained. %, More preferably 0.5% by mass to 40% by mass, and particularly preferably 1% by mass to 30% by mass.
 第4級アンモニウム塩化合物における第4級アンモニウムカチオンは、一価のカチオンであっても、第4級アンモニウム構造を2以上有する二価以上のカチオンであってもよいが、一価のカチオンであることが好ましい。
 上記第4級アンモニウム塩化合物における対アニオンは、電荷を中和できるアニオンであれば、一価のアニオンであっても、二価以上のアニオンであってもよいが、一価のアニオンであることが好ましい。
The quaternary ammonium cation in the quaternary ammonium salt compound may be a monovalent cation or a divalent or higher cation having two or more quaternary ammonium structures, but it is a monovalent cation. It is preferable.
The counter anion in the quaternary ammonium salt compound may be a monovalent anion or a divalent or higher valent anion as long as it is an anion capable of neutralizing the charge, but it is a monovalent anion. Is preferred.
 本開示に係るオニウム塩化合物としては、上記の第4級アンモニウム塩化合物及びスルホニウム塩化合物以外のオニウム塩化合物(以下、「その他のオニウム化合物」ともいう。)であってもよい。
 その他のオニウム塩化合物としては、ジアゾニウム塩化合物、ヨードニウム塩化合物、ピリジニウム塩化合物、アジニウム塩化合物等が挙げられる。
 その他のオニウム塩化合物としては、公知のジアゾニウム塩、ヨードニウム塩、第1級~第3級アンモニウム塩、ピリジニウム塩、アジニウム塩等が挙げられ、中でも、トリアリールスルホニウム、又は、ジアリールヨードニウムのスルホン酸塩、カルボン酸塩、BF 、PF 、ClO などが好ましい。
 本開示において酸発生剤として用い得るオニウム塩化合物としては、下記式(III)又は式(IV)で表されるオニウム塩化合物が挙げられる。
The onium salt compound according to the present disclosure may be an onium salt compound other than the above quaternary ammonium salt compound and sulfonium salt compound (hereinafter, also referred to as “other onium compound”).
Examples of other onium salt compounds include diazonium salt compounds, iodonium salt compounds, pyridinium salt compounds, and azinium salt compounds.
Examples of other onium salt compounds include known diazonium salts, iodonium salts, primary to tertiary ammonium salts, pyridinium salts, azinium salts, and the like. Among them, triarylsulfonium or diaryliodonium sulfonates. , Carboxylate, 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 onium salt compounds represented by the following formula (III) or formula (IV).
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
 上記式(III)中、Ar11とAr12は、それぞれ独立に、置換基を有していてもよい炭素数20個以下のアリール基を示す。このアリール基が置換基を有する場合の好ましい置換基としては、ハロゲン原子、ニトロ基、炭素数12個以下のアルキル基、炭素数12個以下のアルコキシ基、又は炭素数12個以下のアリールオキシ基が挙げられる。Z11-はハロゲン化物イオン、過塩素酸イオン、テトラフルオロボレートイオン、ヘキサフルオロホスフェートイオン、スルホン酸イオン、及び、ペルフルオロアルキルスルホン酸イオン等フッ素原子を有するスルホン酸イオンよりなる群から選択される対イオンを表し、好ましくは、過塩素酸イオン、ヘキサフルオロホスフェートイオン、アリールスルホン酸イオン、及びペルフルオロアルキルスルホン酸である。
 上記式(IV)中、Ar21は、置換基を有していてもよい炭素数1~20のアリール基を示す。好ましい置換基としては、ハロゲン原子、ニトロ基、炭素数1~12のアルキル基、炭素数1~12のアルコキシ基、炭素数1~12のアリールオキシ基、炭素数1~12のアルキルアミノ基、炭素数2~12のジアルキルアミノ基、炭素数6~12のアリールアミノ基又は、ジアリールアミノ基(2つのアリール基の炭素数が、それぞれ独立に、6~12)が挙げられる。Z21-はZ11-と同義の対イオンを表す。
In the above formula (III), Ar 11 and Ar 12 each independently represent an aryl group having 20 or less carbon atoms, which may have a substituent. When the aryl group has 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.
In the formula (IV), 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- .
 上記画像記録層において、好適に用いることのできるオニウム塩化合物の具体例は、国際公開第2016/047392号の段落0121~段落0124に記載された化合物と同様である。 Specific examples of the 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.
 その他のオニウム塩化合物のより好ましい例として、下記化合物(PAG-4)又は(PAG-5)が挙げられる。Meはメチル基を表す。 More preferable examples of other onium salt compounds include the following compounds (PAG-4) or (PAG-5). Me represents a methyl group.
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
<他の樹脂>
 本開示に係る平版印刷版原版は、上記画像記録層に、上記アルカリ可溶性樹脂以外の他の樹脂を更に含んでいてもよい。
 本開示において使用される他の樹脂は、従来公知のものであれば特に制限はなく、公知のアルカリ可溶性樹脂を好ましく用いることができる。
 また、他の樹脂としては、既述のフェノール樹脂が好ましく使用される。なお、他の樹脂におけるフェノール樹脂は、既述のフェノール樹脂と同義であり、好ましい態様も同様である。
<Other resins>
In the lithographic printing plate precursor according to the present disclosure, 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.
As the other resin, the above-mentioned phenol resin is preferably used. The phenol resin in the other resins has the same meaning as the above-mentioned phenol resin, and the preferred embodiments are also the same.
 本開示における画像記録層中の他の樹脂の含有量は、バーニング適性、画像形成性の観点から、上記アルカリ可溶性樹脂の総含有量100質量部に対し、90質量部以下であることが好ましく、50質量部以下であることがより好ましく、30質量部以下であることが特に好ましい。
 本開示において、バーニング処理とは、平版印刷版原版の露光及び現像後に行われる高温加熱処理をいい、バーニング適性に優れるとは、上記バーニング処理後の耐刷性に優れることをいう。
The content of the other resin in the image recording layer in the present disclosure is preferably 90 parts by mass or less based on 100 parts by mass of the total content of the alkali-soluble resin, from the viewpoint of burning suitability and image forming property. The amount is more preferably 50 parts by mass or less, and particularly preferably 30 parts by mass or less.
In the present disclosure, 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.
 上記画像形成層には、所望により他の成分を含有してもよい。
 他の成分としては、公知の添加剤を用いることができる。
 以下、上記画像形成層における任意成分である、酸発生剤、酸増殖剤、及び、その他の添加剤について説明する。
The image 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.
<酸増殖剤>
 本開示における画像記録層は、酸増殖剤を含有してもよい。本開示における酸増殖剤とは、比較的に強い酸の残基で置換された化合物であって、酸触媒の存在下で容易に脱離して新たに酸を発生する化合物である。すなわち、酸触媒反応によって分解し、再び酸を発生する。1反応で1つ以上の酸が増えており、反応の進行に伴って加速的に酸濃度が増加することにより、飛躍的に感度が向上する。この発生する酸の強度は、酸解離定数(pKa)として3以下であることが好ましく、2以下であることがより好ましい。酸解離定数として3以下であれば、酸触媒による脱離反応を引き起こしやすい。
 このような酸触媒に使用される酸としては、ジクロロ酢酸、トリクロロ酢酸、メタンスルホン酸、エタンスルホン酸、ベンゼンスルホン酸、p-トルエンスルホン酸、ナフタレンスルホン酸、フェニルスルホン酸等が挙げられる。
<Acid multiplying agent>
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.
 使用可能な酸増殖剤は、国際公開第2016/047392号の段落0133から段落0135に記載されたものと同様である。 The usable acid multiplying agent is the same as those described in paragraphs 0133 to 0135 of WO 2016/047392.
 これらの酸増殖剤を画像記録層中に添加する場合の含有量としては、画像記録層の全質量に対し、0.01質量%~20質量%が好ましく、0.01質量%~10質量%がより好ましく、0.1質量%~5質量%が更に好ましい。酸増殖剤の含有量が上記範囲において、酸増殖剤を添加する効果が充分に得られ、感度向上が達成されるともに、画像部の膜強度低下が抑制される。 When the acid proliferating agent is added to the image recording layer, 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. When 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.
<その他の添加剤>
 本開示における画像記録層は、その他の添加剤として、現像促進剤、界面活性剤、焼き出し剤、着色剤、可塑剤、ワックス剤等を含んでもよい。
<Other additives>
The image recording layer in the present disclosure may contain a development accelerator, a surfactant, a printout agent, a colorant, a plasticizer, a wax agent, etc. as other additives.
-現像促進剤-
 本開示における画像記録層には、感度を向上させる目的で、酸無水物類、フェノール類、有機酸類を添加してもよい。
 酸無水物類としては環状酸無水物が好ましく、具体的に環状酸無水物としては、米国特許第4,115,128号明細書に記載されている無水フタル酸、テトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、3,6-エンドオキシテトラヒドロ無水フタル酸、テトラクロロ無水フタル酸、無水マレイン酸、クロロ無水マレイン酸、α-フェニル無水マレイン酸、無水コハク酸、無水ピロメリット酸などが使用できる。非環状の酸無水物としては、無水酢酸などが挙げられる。
 フェノール類としては、ビスフェノールA、2,2’-ビスヒドロキシスルホン、p-ニトロフェノール、p-エトキシフェノール、2,4,4’-トリヒドロキシベンゾフェノン、2,3,4-トリヒドロキシベンゾフェノン、4-ヒドロキシベンゾフェノン、4,4’,4”-トリヒドロキシトリフェニルメタン、4,4’,3”,4”-テトラヒドロキシ-3,5,3’,5’-テトラメチルトリフェニルメタンなどが挙げられる。
 有機酸類としては、特開昭60-88942号公報、特開平2-96755号公報などに記載されており、具体的には、p-トルエンスルホン酸、ドデシルベンゼンスルホン酸、p-トルエンスルフィン酸、エチル硫酸、フェニルホスホン酸、フェニルホスフィン酸、リン酸フェニル、リン酸ジフェニル、安息香酸、イソフタル酸、アジピン酸、p-トルイル酸、3,4-ジメトキシ安息香酸、フタル酸、テレフタル酸、4-シクロヘキセン-1,2-ジカルボン酸、エルカ酸、ラウリン酸、n-ウンデカン酸、アスコルビン酸などが挙げられる。上記の酸無水物、フェノール類及び有機酸類の画像記録層の全質量に占める割合は、0.05質量%~20質量%が好ましく、0.1質量%~15質量%がより好ましく、0.1質量%~10質量%が特に好ましい。
-Development accelerator-
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, α-phenylmaleic anhydride, succinic anhydride, pyromellitic anhydride and the like can be used. Acetic anhydride etc. are mentioned as an acyclic acid anhydride.
Examples of 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. Specifically, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, p-toluenesulfinic acid, Ethyl sulfuric acid, phenylphosphonic acid, phenylphosphinic acid, phenyl phosphate, diphenyl phosphate, benzoic acid, isophthalic acid, adipic acid, p-toluic acid, 3,4-dimethoxybenzoic acid, phthalic acid, terephthalic acid, 4-cyclohexene Examples include -1,2-dicarboxylic acid, erucic acid, lauric acid, n-undecanoic acid, 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.
-界面活性剤-
 本開示における画像記録層には、塗布性を良化するため、また、現像条件に対する処理の安定性を広げるため、特開昭62-251740号公報や特開平3-208514号公報に記載されているような非イオン界面活性剤、特開昭59-121044号公報、特開平4-13149号公報に記載されているような両性界面活性剤、特開昭62-170950号公報、特開平11-288093号公報、特開2003-57820号公報に記載されているようなフッ素含有のモノマー共重合体を添加することができる。
 非イオン界面活性剤の具体例としては、ソルビタントリステアレート、ソルビタンモノパルミテート、ソルビタントリオレート、ステアリン酸モノグリセリド、ポリオキシエチレンノニルフェニルエーテル等が挙げられる。
 両性活性剤の具体例としては、アルキルジ(アミノエチル)グリシン、アルキルポリアミノエチルグリシン塩酸塩、2-アルキル-N-カルボキシエチル-N-ヒドロキシエチルイミダゾリニウムベタインやN-テトラデシル-N,N-ベタイン型(例えば、商品名「アモーゲンK」:第一工業製薬(株)製)等が挙げられる。
 界面活性剤の画像記録層の全質量に占める割合は、0.01質量%~15質量%が好ましく、0.01質量%~5質量%がより好ましく、0.05質量%~2.0質量%が更に好ましい。
-Surfactant-
The image recording layer in the present disclosure is described in 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.
Specific examples of the nonionic surfactant include sorbitan tristearate, sorbitan monopalmitate, sorbitan trioleate, stearic acid monoglyceride and polyoxyethylene nonylphenyl ether.
Specific examples of the amphoteric activator include alkyldi (aminoethyl) glycine, alkylpolyaminoethylglycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine and N-tetradecyl-N, N-betaine. Molds (for example, trade name “Amorgen K”: manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) and the like.
The ratio of the surfactant to the total mass of the image recording layer is preferably 0.01% by mass to 15% by mass, more preferably 0.01% by mass to 5% by mass, and 0.05% by mass to 2.0% by mass. % Is more preferable.
-焼出し剤/着色剤-
 上記画像記録層には、露光による加熱後直ちに可視像を得るための焼出し剤や、画像着色剤としての染料や顔料を加えることができる。
 焼出し剤及び着色剤としては、例えば、特開2009-229917号公報の段落0122~0123に詳細に記載され、ここに記載の化合物を本開示においても適用しうる。
 これらの染料は、画像記録層の全質量に対し、0.01質量%~10質量%の割合で添加することが好ましく、0.1質量%~3質量%の割合で添加することがより好ましい。
-Bakeout agent / colorant-
A 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.
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.
These dyes are preferably added in an amount of 0.01% by mass to 10% by mass, more preferably 0.1% by mass to 3% by mass, based on the total mass of the image recording layer. .
-可塑剤-
 上記画像記録層には、塗膜の柔軟性等を付与するために可塑剤を添加してもよい。例えば、ブチルフタリル、ポリエチレングリコール、クエン酸トリブチル、フタル酸ジエチル、フタル酸ジブチル、フタル酸ジヘキシル、フタル酸ジオクチル、リン酸トリクレジル、リン酸トリブチル、リン酸トリオクチル、オレイン酸テトラヒドロフルフリル、アクリル酸又はメタクリル酸のオリゴマー及びポリマー等が用いられる。
 これらの可塑剤は、画像記録層の全質量に対し、0.5質量%~10質量%の割合で添加することが好ましく、1.0質量%~5質量%の割合で添加することがより好ましい。
-Plasticizer-
A plasticizer may be added to the image recording layer in order to impart flexibility to the coating film. For example, butylphthalyl, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, acrylic acid or methacrylic acid. Oligomers and polymers are used.
These 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.
-ワックス剤-
 上記画像記録層には、傷に対する抵抗性を付与する目的で、表面の静摩擦係数を低下させる化合物を添加することもできる。具体的には、米国特許第6,117,913号明細書、特開2003-149799号公報、特開2003-302750号公報、又は、特開2004-12770号公報に記載されているような、長鎖アルキルカルボン酸のエステルを有する化合物などを挙げることができる。
 添加量として好ましいのは、画像記録層の全質量中に占める割合が、0.1質量%~10質量%であることが好ましく、0.5質量%~5質量%であることがより好ましい。
-Wax agent-
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. Specifically, as described in US Pat. No. 6,117,913, JP-A 2003-149799, JP-A 2003-302750, or JP-A 2004-12770, Examples thereof include compounds having an ester of a long-chain alkylcarboxylic acid.
The addition amount 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.
<下層及び上層>
 また、上記画像記録層は、上層及び下層を有することが好ましく、支持体上に下層及び上層をこの順に配設した画像記録層(以下、「2層構造の平版印刷版原版」ともいう。)であることがより好ましい。
 下層及び上層は、2つの層を分離して形成することが好ましい。
 2つの層を分離して形成する方法としては、例えば、下層に含まれる成分と、上層に含まれる成分との溶剤溶解性の差を利用する方法、又は、上層を塗布した後、急速に溶剤を乾燥、除去する方法等が挙げられる。後者の方法を併用することにより、層間の分離が一層良好に行われることになるため好ましい。
 上記アルカリ可溶性樹脂、特定高分子化赤外線吸収剤、及び、オニウム塩化合物は、下層又は上層のいずれかに含まれていればよいが、耐刷性及び耐傷性の観点から、上層が、特定高分子化赤外線吸収剤、及び、オニウム塩化合物を少なくとも含み、かつ、下層が、アルカリ可溶性樹脂を少なくとも含むことが好ましい。
 以下、これらの方法について詳述するが、2つの層を分離して塗布する方法はこれらに限定されるものではない。
<Lower layer and upper layer>
Further, 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.
As 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. It is preferable to use the latter method together because the separation between layers can be more favorably performed.
The alkali-soluble resin, the specific polymerized infrared absorber, and the onium salt compound may be contained in either the lower layer or the upper layer, but from the viewpoint of printing durability and scratch resistance, the upper layer has a specific height. It is preferable that at least the molecularized infrared absorber and the onium salt compound are contained, and that the lower layer contains at least an alkali-soluble resin.
Hereinafter, these methods will be described in detail, but the method of separating and applying the two layers is not limited thereto.
 下層に含まれる成分と上層に含まれる成分との溶剤溶解性の差を利用する方法としては、上層用塗布液を塗布する際に、下層に含まれる成分のいずれもが不溶な溶剤系を用いるものである。これにより、二層塗布を行っても、各層を明確に分離して塗膜にすることが可能になる。例えば、下層成分として、上層成分であるアルカリ可溶性樹脂を溶解するメチルエチルケトンや1-メトキシ-2-プロパノール等の溶剤に不溶な成分を選択し、上記下層成分を溶解する溶剤系を用いて下層を塗布、乾燥し、その後、アルカリ可溶性樹脂を主体とする上層をメチルエチルケトンや1-メトキシ-2-プロパノール等で溶解し、塗布、乾燥することにより二層化が可能になる。 As a method of utilizing the difference in solvent solubility between the component contained in the lower layer and the component contained in the upper layer, a solvent system in which 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. For example, as the lower layer component, 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. After drying, 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.
 次に、2層目(上層)を塗布後に、極めて速く溶剤を乾燥させる方法としては、ウェブの走行方向に対してほぼ直角に設置したスリットノズルより高圧エアーを吹きつけることや、蒸気等の加熱媒体を内部に供給されたロール(加熱ロール)よりウェブの下面から伝導熱として熱エネルギーを与えること、あるいはそれらを組み合わせることにより達成できる。 Next, as a method for drying the solvent extremely quickly after applying the second layer (upper 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.
 本開示に係る平版印刷版原版の支持体上に塗布される下層成分の乾燥後の塗布量は、0.5g/m~4.0g/mの範囲にあることが好ましく、0.6g/m~2.5g/mの範囲にあることがより好ましい。0.5g/m以上であると、耐刷性に優れ、4.0g/m以下であると、画像再現性及び感度に優れる。
 また、上層成分の乾燥後の塗布量は、0.05g/m~1.0g/mの範囲にあることが好ましく、0.08g/m~0.7g/mの範囲であることがより好ましい。0.05g/m以上であると、現像ラチチュード、及び、耐傷性に優れ、1.0g/m以下であると、感度に優れる。
 下層及び上層を合わせた乾燥後の塗布量としては、0.6g/m~4.0g/mの範囲にあることが好ましく、0.7g/m~2.5g/mの範囲にあることがより好ましい。0.6g/m以上であると、耐刷性に優れ、4.0g/m以下であると、画像再現性及び感度に優れる。
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. If it is 0.05 g / m 2 or more, development latitude, and excellent scratch resistance, if it is 1.0 g / m 2 or less, excellent sensitivity.
The 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. When it is 0.6 g / m 2 or more, printing durability is excellent, and when it is 4.0 g / m 2 or less, image reproducibility and sensitivity are excellent.
〔支持体〕
 本開示に係る平版印刷版原版に使用される支持体としては、必要な強度と耐久性を備えた寸度的に安定な板状物であれば特に制限はなく、例えば、紙、プラスチック(例えば、ポリエチレン、ポリプロピレン、ポリスチレン等)がラミネートされた紙、金属板(例えば、アルミニウム、亜鉛、銅等)、プラスチックフィルム(例えば、二酢酸セルロース、三酢酸セルロース、プロピオン酸セルロース、酪酸セルロース、酢酸酪酸セルロース、硝酸セルロース、ポリエチレンテレフタレート、ポリエチレン、ポリスチレン、ポリプロピレン、ポリカーボネート、ポリビニルアセタール等)、上記の如き金属がラミネート若しくは蒸着された紙、又は、プラスチックフィルム等が挙げられる。
[Support]
The support used in the lithographic printing plate precursor according to the present disclosure is not particularly limited as long as it is a dimensionally stable plate-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.
 上記支持体としては、ポリエステルフィルム又はアルミニウム板が好ましく、その中でも寸度安定性がよく、比較的安価であるアルミニウム板は特に好ましい。好適なアルミニウム板は、純アルミニウム板及びアルミニウムを主成分とし、微量の異元素を含む合金板であり、更にアルミニウムがラミネート又は蒸着されたプラスチックフィルムでもよい。アルミニウム合金に含まれる異元素には、ケイ素、鉄、マンガン、銅、マグネシウム、クロム、亜鉛、ビスマス、ニッケル、チタンなどがある。合金中の異元素の含有量は10質量%以下であることが好ましい。 As the above support, 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.
 本開示において特に好適なアルミニウムは、純アルミニウムであるが、完全に純粋なアルミニウムは精錬技術上製造が困難であるので、僅かに異元素を含有するものでもよい。
 このように本開示に適用されるアルミニウム板は、その組成が特定されるものではなく、従来より公知公用の素材のアルミニウム板を適宜に利用することができる。本開示において用いられるアルミニウム板の厚みは、0.1mm~0.6mmであることが好ましく、0.15mm~0.4mmであることがより好ましく、0.2mm~0.3mmであることが特に好ましい。
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.
As described above, 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.
 このようなアルミニウム板には、必要に応じて粗面化処理、陽極酸化処理などの表面処理を行ってもよい。アルミニウム支持体の表面処理については、例えば、特開2009-175195号公報の段落0167~0169に詳細に記載されるような、界面活性剤、有機溶剤又はアルカリ性水溶液などによる脱脂処理、表面の粗面化処理、陽極酸化処理などが適宜、施される。
 陽極酸化処理を施されたアルミニウム表面は、必要により親水化処理が施される。
 親水化処理としては、2009-175195号公報の段落0169に開示されているような、アルカリ金属シリケート(例えばケイ酸ナトリウム水溶液)法、フッ化ジルコン酸カリウムあるいは、ポリビニルホスホン酸で処理する方法などが用いられる。
 また、特開2011-245844号公報に記載された支持体も好ましく用いられる。
Such aluminum plate may be subjected to surface treatment such as surface roughening treatment and anodizing treatment, if necessary. Regarding the surface treatment of the aluminum support, for example, 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.
Examples of the hydrophilic treatment 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.
〔下塗層〕
 本開示に係る平版印刷版原版は、必要に応じて、支持体と画像形成層との間に、下塗層を設けることができる。
 下塗層成分としては、種々の有機化合物が用いられ、例えば、カルボキシメチルセルロース、デキストリン等のアミノ基を有するホスホン酸類、有機ホスホン酸、有機リン酸、有機ホスフィン酸、アミノ酸類、並びに、ヒドロキシ基を有するアミンの塩酸塩等が好ましく挙げられる。また、これら下塗層成分は、1種単独で用いても、2種以上混合して用いてもよい。下塗層に使用される化合物の詳細、下塗層の形成方法は、特開2009-175195号公報の段落0171~0172に記載され、これらの記載は本開示にも適用される。
 下塗層の被覆量は、2mg/m~200mg/mであることが好ましく、5mg/m~100mg/mであることがより好ましい。被覆量が上記範囲であると、十分な耐刷性能が得られる。
[Undercoat layer]
In the lithographic printing plate precursor according to the present disclosure, an undercoat layer can be provided between the support and the image forming layer, if necessary.
As the undercoat layer component, 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. Details of the compound used for the undercoat layer and the method for forming the undercoat layer are described in paragraphs 0171 to 0172 of JP2009-175195A, and these descriptions also apply to the present disclosure.
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.
〔バックコート層〕
 本開示に係る平版印刷版原版における上記支持体の上記画像記録層が設けられた側とは反対の面には、必要に応じてバックコート層が設けられることが好ましい。かかるバックコート層としては、特開平5-45885号公報記載の有機高分子化合物及び特開平6-35174号公報記載の有機又は無機金属化合物を加水分解及び重縮合させて得られる金属酸化物からなる被覆層が好ましく用いられる。これらの被覆層のうち、Si(OCH、Si(OC、Si(OC、Si(OCなどのケイ素のアルコキシ化合物が安価で入手し易く、それから得られる金属酸化物の被覆層が耐現像液に優れており特に好ましい。
[Backcoat layer]
In the planographic printing plate precursor according to the present disclosure, a back coat layer is preferably provided on the surface of the support opposite to the side on which the image recording layer is provided, if necessary. 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. Among these coating layers, silicon alkoxy compounds such as Si (OCH 3 ) 4 , Si (OC 2 H 5 ) 4 , Si (OC 3 H 7 ) 4 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.
(平版印刷版の作製方法)
 本開示に係る平版印刷版の作製方法は、本開示に係る平版印刷版原版を画像様に露光する露光工程、及び、現像液を用いて現像する現像工程、をこの順で含む。
 上記現像液としては、シリケートカスの抑制の観点から、pH9以上のアルカリ現像液であることが好ましい。
 また、本開示に係る平版印刷版の作製方法は、シリケートカスの抑制の観点から、本開示に係る平版印刷版原版を赤外線レーザーを用いて画像様に露光する工程、及び、シリケート化合物を含まないpH9以上のアルカリ現像液を用いて現像する工程を含むことが好ましい。
 以下、本開示に係る平版印刷版の作製方法の各工程について詳細に説明する。
(Method of preparing lithographic printing plate)
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.
Further, 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.
Hereinafter, each step of the method for producing a lithographic printing plate according to the present disclosure will be described in detail.
<露光工程>
 本開示に係る平版印刷版の作製方法は、本開示に係る平版印刷版原版を画像様に露光する露光工程を含む。
 本開示に係る平版印刷版原版の画像露光に用いられる活性光線の光源としては、近赤外から赤外領域に発光波長を持つ光源が好ましく、固体レーザー、半導体レーザーがより好ましい。中でも、本開示においては、波長750nm~1,400nmの赤外線を放射する固体レーザー又は半導体レーザーにより画像露光されることが特に好ましい。
 レーザーの出力は、100mW以上が好ましく、露光時間を短縮するため、マルチビームレーザデバイスを用いることが好ましい。また、1画素あたりの露光時間は20μ秒以内であることが好ましい。
 平版印刷版原版に照射されるエネルギーは、10mJ/cm~300mJ/cmであることが好ましい。上記範囲であると、硬化が十分に進行し、また、レーザーアブレーションを抑制し、画像が損傷を防ぐことができる。
<Exposure process>
The method for producing a lithographic printing plate according to the present disclosure includes an exposure step of imagewise exposing the lithographic printing plate precursor according to the present disclosure.
As 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. Among them, in the present disclosure, it is particularly preferable to perform image exposure with a solid-state laser or semiconductor laser that emits infrared rays having a wavelength of 750 nm to 1,400 nm.
The laser output is preferably 100 mW or more, and 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 μsec.
The energy applied to the lithographic printing plate precursor is preferably 10 mJ / cm 2 to 300 mJ / cm 2 . When the content is in the above range, curing can be sufficiently advanced, laser ablation can be suppressed, and damage to an image can be prevented.
 本開示における露光は、光源の光ビームをオーバーラップさせて露光することができる。オーバーラップとは、副走査ピッチ幅がビーム径より小さいことをいう。オーバーラップは、例えば、ビーム径をビーム強度の半値幅(FWHM)で表したとき、FWHM/副走査ピッチ幅(オーバーラップ係数)で定量的に表現することができる。本開示ではこのオーバーラップ係数が、0.1以上であることが好ましい。 The exposure in the present disclosure can be performed by overlapping the light beams of the light 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.
 本開示において使用することができる露光装置の光源の走査方式は、特に限定はなく、円筒外面走査方式、円筒内面走査方式、平面走査方式などを用いることができる。また、光源のチャンネルは単チャンネルでもマルチチャンネルでもよいが、円筒外面方式の場合にはマルチチャンネルが好ましく用いられる。 The light source scanning method of the exposure apparatus that can be used in the present disclosure is not particularly limited, and a 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.
<現像工程>
 本開示に係る平版印刷版の作製方法は、現像液を用いて現像する現像工程を含む。
 現像工程に使用される現像液は、pH9以上のアルカリ現像液が好ましく、シリケート化合物を含まないpH9以上のアルカリ現像液がより好ましい。
 上記シリケート化合物としては、二酸化ケイ素が挙げられ、上記シリケート化合物を含まない現像液をノンシリケート現像液ともいい、ノンシリケート現像液を用いる現像をノンシリケート現像ともいう。
 シリケート化合物を含まない現像液を用いることにより、現像カス抑制性に優れる。
 また、上記ノンシリケート現像液としては、特開2001-209172号公報に記載の非シリケート現像液が好適に用いられる。
 上記アルカリ現像液のpHは、12.5~13.5であることが好ましい。
<Developing process>
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.
Examples of 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.
By using a developer that does not contain a silicate compound, the development dust suppressing property is excellent.
As 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.
 上記アルカリ現像液は、緩衝作用を有する有機化合物、及び、塩基性化合物を含むことが好ましい。
 緩衝作用を有する有機化合物としては、特開平8-220775号公報に緩衝作用を有する化合物として記載されている糖類(特に一般式(I)又は(II)で表されるもの)、オキシム類(特に一般式(III)で表されるもの)、フェノール類(特に一般式(IV)で表されるもの)及びフッ素化アルコール類(特に一般式(V)で表されるもの)等が挙げられる。一般式(I)~(V)で表される化合物のなかでも、好ましいものは、一般式(I)又は(II)で表される糖類、一般式(V)で表されるフェノール類であり、更に好ましくは一般式(I)又は(II)で表される糖類のうち、サッカロース等の非還元糖又はスルホサリチル酸である。上記非還元糖には、還元基同士の結合したトレハロース型少糖類、糖類の還元基と非糖類が結合した配糖体、糖類に水素添加して還元した糖アルコール等が包含される。
The alkaline developer preferably contains an organic compound having a buffering action and a basic compound.
Examples of 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. Among 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). Of the saccharides represented by the general formula (I) or (II), 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.
 上記トレハロース型少糖類としては、例えば、サッカロースやトレハロースが挙げられ、上記配糖体としては、例えば、アルキル配糖体、フェノール配糖体、カラシ油配糖体等が挙げられる。上記糖アルコールとしては、例えば、D,L-アラビット、リビット、キシリット、D,L-ソルビット、D,L-アンニット、D,L-イジット、D,L-タリット、ズリシット、アロズルシット等が挙げられる。更には、二糖類の水素添加で得られるマルチトール、オリゴ糖の水素添加で得られる還元体(還元水あめ)等も好適に挙げることができる。 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, zuricit, and alodulcit. Furthermore, 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.
 上記のうち、非還元糖としては、糖アルコール、サッカロースが好ましく、中でも特に、D-ソルビット、サッカロース、還元水あめが、適度なpH領域に緩衝作用がある点でより好ましい。 Among the above, 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.
 上記緩衝作用を有する有機化合物は、1種単独で使用しても、2種以上を併用してもよい。
 上記緩衝作用を有する有機化合物の含有量は、現像液の全質量に対し、0.1質量%~30質量%が好ましく、1質量%~20質量%がより好ましい。
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.
 上記緩衝作用を有する有機化合物には、塩基性化合物としてアルカリ剤を、従来公知のものの中から適宜選択して組合せることができる。
 上記アルカリ剤としては、例えば、水酸化ナトリウム、水酸化カリウム、水酸化リチウム、リン酸三ナトリウム、リン酸三カリウム、リン酸三アンモニウム、リン酸二ナトリウム、リン酸二カリウム、リン酸二アンモニウム、炭酸ナトリウム、炭酸カリウム、炭酸アンモニウム、炭酸水素ナトリウム、炭酸水素カリウム、炭酸水素アンモニウム、ホウ酸ナトリウム、ホウ酸カリウム、ホウ酸アンモニウム等の無機アルカリ剤、クエン酸カリウム、クエン酸三カリウム、クエン酸ナトリウム等が挙げられる。更に、モノメチルアミン、ジメチルアミン、トリメチルアミン、モノエチルアミン、ジエチルアミン、トリエチルアミン、モノイソプロピルアミン、ジイソプロピルアミン、トリイソプロピルァミン、n-ブチルアミン、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、モノイソプロパノールアミン、ジイソブロパノールアミシ、エチレンイミン、エチレンジアミン、ピリジン等の有機アルカリ剤も好適に挙げることができる。
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.
Examples of 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. Furthermore, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanol. Preference is also given to organic alkali agents such as neuramis, ethyleneimine, ethylenediamine, pyridine and the like.
 中でも、上記塩基性化合物としては、水酸化ナトリウム、又は、水酸化カリウムが好ましい。その理由は、非還元糖に対する添加量を調整することにより、広いpH領域においてpH調整が可能となるためである。
 また、リン酸三ナトリウム、リン酸三カリウム、炭酸ナトリウム、炭酸カリウム等もそれ自身に緩衝作用があるので好ましい。
Among them, 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.
In addition, trisodium phosphate, tripotassium phosphate, sodium carbonate, potassium carbonate and the like are preferable because they have a buffering effect.
 上記塩基性化合物は、1種単独で用いても、2種以上を併用してもよい。
 上記塩基性化合物の含有量は、特に制限はなく、所望のpHとなる量を現像液に添加すればよい。
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.
 上記現像液は、処理性の観点から、界面活性剤を含むことが好ましい。
 上記現像液に用いられる界面活性剤は、アニオン性、ノニオン性、カチオン性、及び、両性の界面活性剤のいずれも用いることができるが、既述のように、アニオン性、ノニオン性の界面活性剤が好ましい。
 本開示において現像液に用いられるアニオン性、ノニオン性、カチオン性、及び、両性界面活性剤としては、特開2013-134341号公報の段落0128~0131に記載の物を使用することができる。
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.
As the 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.
 また、水に対する安定な溶解性あるいは混濁性の観点から、上記界面活性剤のHLB値が、6以上であることが好ましく、8以上であることがより好ましい。
 上記現像液に用いられる界面活性剤としては、アニオン性界面活性剤及びノニオン界面活性剤が好ましく、スルホン酸又はスルホン酸塩を含有するアニオン性界面活性剤及び、芳香環とエチレンオキサイド鎖を有するノニオン界面活性剤が特に好ましい。
 界面活性剤は、単独又は組み合わせて使用することができる。
 界面活性剤の現像液中における含有量は、0.01質量%~10質量%が好ましく、0.01質量%~5質量%がより好ましい。
From the viewpoint of stable solubility or turbidity in water, the HLB value of the surfactant is preferably 6 or more, more preferably 8 or more.
As the surfactant used in the developing solution, 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.
 上記現像液には上記の他に、湿潤剤、防腐剤、キレート化合物、消泡剤、有機酸、有機溶剤、無機酸、無機塩などを含有することができる。ただし、水溶性高分子化合物を添加すると、特に現像液が疲労した際に版面がベトツキやすくなるため、添加しないことが好ましい。 In addition to the above, 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. However, when the water-soluble polymer compound is added, the plate surface tends to become sticky, especially when the developer is fatigued.
 湿潤剤としては、特開2013-134341号公報の段落0141に記載の湿潤剤を好適に用いることができる。湿潤剤は単独で用いてもよいが、2種以上併用してもよい。湿潤剤は、現像剤の全質量に対し、0.1質量%~5質量%の量で使用されることが好ましい。 As the wetting agent, the wetting agent described in paragraph 0141 of JP2013-134341A can be 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.
 防腐剤としては、特開2013-134341号公報の段落0142に記載の防腐剤を好適に用いることができる。種々のカビ、殺菌に対して効力のあるように2種以上の防腐剤を併用することが好ましい。防腐剤の添加量は、細菌、カビ、酵母等に対して、安定に効力を発揮する量であって、細菌、カビ、酵母の種類によっても異なるが、現像液の全質量に対して、0.01質量%~4質量%の範囲が好ましい。 As the preservative, the preservative described in paragraph 0142 of JP2013-134341A can be 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.
 キレート化合物としては、特開2013-134341号公報の段落0143に記載のキレート化合物を好適に用いることができる。キレート剤は現像液組成中に安定に存在し、印刷性を阻害しないものが選ばれる。添加量は、現像液の全質量に対して、0.001質量%~1.0質量%が好適である。 As the chelate compound, 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.
 消泡剤としては、特開2013-134341号公報の段落0144に記載の消泡剤を好適に用いることができる。消泡剤の含有量は、現像液の全重量に対して、0.001質量%~1.0質量%の範囲が好適である。 As the defoaming agent, 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.
 有機酸としては、特開2013-134341号公報の段落0145に記載の消泡剤を好適に用いることができる。有機酸の含有量は、現像液の全質量に対して、0.01質量%~0.5質量%が好ましい。 As the organic acid, 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.
 有機溶剤としては、例えば、脂肪族炭化水素類(ヘキサン、ヘプタン、“アイソパーE、H、G”(エッソ化学(株)製)、ガソリン、若しくは、灯油等)、芳香族炭化水素類(トルエン、キシレン等)、又は、ハロゲン化炭化水素(メチレンジクロライド、エチレンジクロライド、トリクレン、モノクロルベンゼン等)や、極性溶剤が挙げられる。 Examples of the organic solvent include aliphatic hydrocarbons (hexane, heptane, “Isopar E, H, G” (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.
 極性溶剤としては、アルコール類(メタノール、エタノール、プロパノール、イソプロパノール、ベンジルアルコール、エチレングリコールモノメチルエーテル、2-エトキシエタノール等)、ケトン類(メチルエチルケトン、シクロヘキサノン等)、エステル類(酢酸エチル、乳酸メチル、プロピレングリコールモノメチルエーテルアセテート等)、その他(トリエチルホスフェート、トリクレジルホスフェート、N-フェニルエタノールアミン、N-フェニルジエタノールアミン等)等が挙げられる。 Examples of polar solvents include alcohols (methanol, ethanol, propanol, isopropanol, benzyl alcohol, ethylene glycol monomethyl ether, 2-ethoxyethanol, etc.), ketones (methyl ethyl ketone, cyclohexanone, etc.), esters (ethyl acetate, methyl lactate, propylene). Glycol monomethyl ether acetate, etc.) and others (triethyl phosphate, tricresyl phosphate, N-phenylethanolamine, N-phenyldiethanolamine, etc.) and the like.
 また、上記有機溶剤が水に不溶な場合は、界面活性剤等を用いて水に可溶化して使用することも可能である。現像液が有機溶剤を含有する場合は、安全性、引火性の観点から、溶剤の濃度は40質量%未満が好ましい。 If the above organic solvent is insoluble in water, it can be solubilized in water with a surfactant or the like before use. When the developer contains an organic solvent, the concentration of the solvent is preferably less than 40 mass% from the viewpoint of safety and flammability.
 無機酸及び無機塩としては、リン酸、メタリン酸、第一リン酸アンモニウム、第二リン酸アンモニウム、第一リン酸ナトリウム、第二リン酸ナトリウム、第一リン酸カリウム、第二リン酸カリウム、トリポリリン酸ナトリウム、ピロリン酸カリウム、ヘキサメタリン酸ナトリウム、硝酸マグネシウム、硝酸ナトリウム、硝酸カリウム、硝酸アンモニウム、硫酸ナトリウム、硫酸カリウム、硫酸アンモニウム、亜硫酸ナトリウム、亜硫酸アンモニウム、硫酸水素ナトリウム、硫酸ニッケルなどが挙げられる。無機塩の含有量は、現像液の全質量に対し、0.01質量%~0.5質量%が好ましい。 As 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.
 現像の温度は、現像可能であれば特に制限はないが、60℃以下であることが好ましく、15℃~40℃であることがより好ましい。自動現像機を用いる現像処理においては、処理量に応じて現像液が疲労してくることがあるので、補充液又は新鮮な現像液を用いて処理能力を回復させてもよい。現像及び現像後の処理の一例としては、アルカリ現像を行い、後水洗工程でアルカリを除去し、ガム引き工程でガム処理を行い、乾燥工程で乾燥する方法が例示できる。また、他の例としては、炭酸イオン、炭酸水素イオン及び界面活性剤を含有する水溶液を用いることにより、前水洗、現像及びガム引きを同時に行う方法が好ましく例示できる。よって、前水洗工程は特に行わなくともよく、一液を用いるだけで、更には一浴で前水洗、現像及びガム引きを行ったのち、乾燥工程を行うことが好ましい。現像の後は、スクイズローラ等を用いて余剰の現像液を除去してから乾燥を行うことが好ましい。 The 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. In a developing process using an automatic developing machine, 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. As an example of the development and the treatment after the development, 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. As another example, 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.
 現像工程は、擦り部材を備えた自動処理機により好適に実施することができる。自動処理機としては、例えば、画像露光後の平版印刷版原版を搬送しながら擦り処理を行う、特開平2-220061号公報、特開昭60-59351号公報に記載の自動処理機や、シリンダー上にセットされた画像露光後の平版印刷版原版を、シリンダーを回転させながら擦り処理を行う、米国特許第5148746号、同5568768号、英国特許2297719号の各明細書に記載の自動処理機等が挙げられる。中でも、擦り部材として、回転ブラシロールを用いる自動処理機が特に好ましい。 Development process can be preferably carried out by an automatic processor equipped with a rubbing member. As 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, the automatic processor described in each specification of US Pat. Nos. 5,148,746, 5,568,768 and British Patent 2,297,719. Is mentioned. Above all, an automatic processor using a rotating brush roll as the rubbing member is particularly preferable.
 本開示において使用する回転ブラシロールは、画像部の傷つき難さ、更には、平版印刷版原版の支持体における腰の強さ等を考慮して適宜選択することができる。回転ブラシロールとしては、ブラシ素材をプラスチック又は金属のロールに植え付けて形成された公知のものが使用できる。例えば、特開昭58-159533号公報、特開平3-100554号公報に記載のものや、実公昭62-167253号公報に記載されているような、ブラシ素材を列状に植え込んだ金属又はプラスチックの溝型材を芯となるプラスチック又は金属のロールに隙間なく放射状に巻き付けたブラシロールが使用できる。
 ブラシ素材としては、プラスチック繊維(例えば、ポリエチレンテレフタレート、ポリブチレンテレフタレート等のポリエステル系、ナイロン6.6、ナイロン6.10等のポリアミド系、ポリアクリロニトリル、ポリ(メタ)アクリル酸アルキル等のポリアクリル系、ポリプロピレン、ポリスチレン等のポリオレフィン系の合成繊維)を使用することができ、例えば、繊維の毛の直径は20μm~400μm、毛の長さは5mm~30mmのものが好適に使用できる。
 回転ブラシロールの外径は30mm~200mmが好ましく、版面を擦るブラシの先端の周速は0.1m/sec~5m/secが好ましい。回転ブラシロールは、複数本用いることが好ましい。
The rotating brush roll used in the present disclosure can be appropriately selected in consideration of the scratch resistance of the image area, the rigidity of the support of the planographic printing plate precursor, and the like. As the rotating brush roll, a known roll formed by planting a brush material on a plastic or metal roll can be used. For example, 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.
As the brush material, 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) can be preferably used. For example, fibers having a hair diameter of 20 μm to 400 μm 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.
 回転ブラシロールの回転方向は、平版印刷版原版の搬送方向に対し、同一方向であっても、逆方向であってもよいが、2本以上の回転ブラシロールを使用する場合は、少なくとも1本の回転ブラシロールが同一方向に回転し、少なくとも1本の回転ブラシロールが逆方向に回転することが好ましい。これにより、非画像部の画像記録層の除去が更に確実となる。更に、回転ブラシロールをブラシロールの回転軸方向に揺動させることも効果的である。 The rotating 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.
<制御工程>
 本開示に係る平版印刷版の作製方法は、上記アルカリ現像液の液活性を、上記アルカリ現像液の電導度で測定し、測定された測定値に従って補充液を加えて、目標の電導度となるように調整し、液活性を制御する工程(「制御工程」ともいう。)を含むことが好ましい。
 なお、上記制御工程におけるアルカリ現像液は、シリケート化合物を含まないpH9以上のアルカリ現像液であることが好ましい。
 本開示において、「補充液」とは、現像性能を一定に保つために補充する処理液のことである。一般に、この補充液として、補充液原液を希釈液(例、水)で希釈して調製されたものや、希釈することなく補充液原液そのままを用いるものがあるが、本開示では、上記補充液は、補充液原液を希釈液で希釈し調製したものであることが好ましい。また、補充方法としては、予め希釈して調製した補充液を現像液に補充することもあれば、補充液原液と希釈液とを別々に直接現像液に補充する方法もある。
<Control process>
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.
In the present disclosure, the “replenisher” is a processing solution replenished to keep the developing performance constant. In general, as 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. As 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.
 また、上記アルカリ現像液の電導度の測定方法としては、電導度センサを用いることが好ましい。
 現像液の電導度を測定する電導度センサとしては、交流電導度計、交流ブリッジ計あるいは、その他の電導度計などの公知の手段を用いることができる。また、上記測定装置の測定電流値や発振周波数等は、現像液の組成等により最適条件は異なるが、電流値は装置的にも又水溶性の現像液の電気分解を防ぐためにもある程度低いことが好ましく、数百mA~数μAが好ましい。また、周波数は、現像液中の静電容量成分との関係から、数百Hz~数百kHzのものが好ましい。
As a method for measuring the electric conductivity of the alkaline developer, it is preferable to use an electric conductivity sensor.
As 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. Further, 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 μA is preferable. Further, the frequency is preferably several hundreds Hz to several hundreds kHz from the relationship with the electrostatic capacitance component in the developing solution.
 電解質を含む現像液の電導度の値は、水溶液の温度に依存し、液温が上がるとその値は低下する。したがって、より好ましくは、温度センサ及び温度補償回路を付した測定器で電導度を測定するのが好ましい。また、補充を制御する制御装置において、実際に測定した液抵抗値と液温度から、予め定めた温度における電導度値に換算し温度補償することも可能である。交流電導度計、交流ブリッジ計又は、その他の電導度計のセンサ設置位置は、測定時に現像液に浸漬され、現像液の交流電導度値が測定できる場所であればよく、例えば自動現像装置液の現像液循環系、特に現像タンク中、又は、循環パイプ中が好ましい位置である。検出部としては、電極に白金、ステンレス等を用いた公知の測定セルを使用することができる。 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, 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, for example, an automatic developing device solution. 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.
 また、上記制御工程としては、特開2005-275384号公報を参照することができる。 For the control process, reference can be made to JP-A-2005-275384.
 現像工程の後、連続的又は不連続的に乾燥工程を設けることが好ましい。乾燥は熱風、赤外線、遠赤外線等によって行う。
 本開示に係る平版印刷版の作製方法において好適に用いられる自動処理機としては、現像部と乾燥部とを有する装置が用いられ、平版印刷版原版に対して、現像槽で、現像とガム引きとが行われ、その後、乾燥部で乾燥されて平版印刷版が得られる。
After the developing step, it is preferable to provide a drying step continuously or discontinuously. Drying is performed with hot air, infrared rays, far infrared rays, or the like.
As 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.
 また、耐刷性等の向上を目的として、現像後の印刷版を加熱することもできる。加熱温度は、200℃~500℃の範囲であることが好ましい。
 このようにして得られた平版印刷版は、オフセット印刷機に掛けられ、多数枚の印刷に好適に用いられる。
Further, 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 lithographic printing plate thus obtained is set on an offset printing machine and is suitably used for printing a large number of sheets.
 以下、実施例により本開示を詳細に説明するが、本開示はこれらに限定されるものではない。なお、本実施例において、「%」、「部」とは、特に断りのない限り、それぞれ「質量%」、「質量部」を意味する。
 また、高分子化合物において、特別に規定したもの以外は、分子量は重量平均分子量(Mw)であり、構成単位の比率はモル百分率である。また、重量平均分子量(Mw)は、ゲル浸透クロマトグラフィー(GPC)法によるポリスチレン換算値として測定した値である。
Hereinafter, the present disclosure will be described in detail with reference to Examples, but the present disclosure is not limited thereto. In this example, "%" and "part" mean "mass%" and "part by mass", respectively, unless otherwise specified.
In addition, in the polymer compound, 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. The weight average molecular weight (Mw) is a value measured as a polystyrene conversion value by a gel permeation chromatography (GPC) method.
<支持体の作製>
 Si:0.06質量%、Fe:0.30質量%、Cu:0.025質量%、Mn:0.001質量%、Mg:0.001質量%、Zn:0.001質量%、Ti:0.03質量%を含有し、残部はAlと不可避不純物のアルミニウム合金を用いて溶湯を調製し、溶湯処理及びろ過を行った上で、厚さ500mm、幅1,200mmの鋳塊をダイレクトチル(DC)鋳造法で作製した。表面を平均10mmの厚さで面削機により削り取った後、550℃で、約5時間均熱保持し、温度400℃に下がったところで、熱間圧延機を用いて厚さ2.7mmの圧延板とした。更に、連続焼鈍機を用いて熱処理を500℃で行った後、冷間圧延で、厚さ0.24mmに仕上げ、JIS 1050材のアルミニウム板を得た。なお、得られたアルミニウムの平均結晶粒径の短径は50μm、長径は300μmであった。このアルミニウム板を幅1,030mmにした後、以下に示す表面処理に供した。
<Preparation of support>
Si: 0.06 mass%, Fe: 0.30 mass%, Cu: 0.025 mass%, Mn: 0.001 mass%, Mg: 0.001 mass%, Zn: 0.001 mass%, Ti: It contains 0.03% by mass, the balance is Al and aluminum alloy of unavoidable impurities, prepares a molten metal, and after the molten metal treatment and filtration, the ingot with a thickness of 500 mm and a width of 1,200 mm is directly chilled. It was produced by the (DC) casting method. After shaving the surface with an average thickness of 10 mm by a chamfering machine, it was soaked and held at 550 ° C. for about 5 hours, and when the temperature fell to 400 ° C., it was rolled with a hot rolling mill to a thickness of 2.7 mm. It was a plate. Further, heat treatment was performed at 500 ° C. using a continuous annealing machine, and then cold rolling was performed to finish the thickness to 0.24 mm to obtain a JIS 1050 aluminum plate. The average crystal grain size of the obtained aluminum had a short diameter of 50 μm and a long diameter of 300 μm. After making this aluminum plate a width of 1,030 mm, it was subjected to the following surface treatment.
<表面処理>
 表面処理は、以下の(a)~(k)の各種処理を連続的に行った。なお、各処理及び水洗の後には、ニップローラーで液切りを行った。
<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.
(a)機械的粗面化処理
 図1に示したような装置を使って、比重1.12の研磨剤(パミス)と水との懸濁液を研磨スラリー液としてアルミニウム板の表面に供給しながら、回転するローラ状ナイロンブラシにより機械的粗面化処理を行った。図1において、1はアルミニウム板、2及び4はローラ状ブラシ、3は研磨スラリー液、5、6、7及び8は支持ローラである。研磨剤の平均粒径は30μm、最大粒径は100μmであった。ナイロンブラシの材質は6・10ナイロン、毛長は45mm、毛の直径は0.3mmであった。ナイロンブラシはφ300mmのステンレス製の筒に穴をあけて密になるように植毛した。回転ブラシは3本使用した。ブラシ下部の2本の支持ローラ(φ200mm)の距離は300mmであった。ブラシローラはブラシを回転させる駆動モータの負荷が、ブラシローラをアルミニウム板に押さえつける前の負荷に対して7kWプラスになるまで押さえつけた。ブラシの回転方向はアルミニウム板の移動方向と同じであった。ブラシの回転数は200rpm(revolutions per minute)であった。
(A) 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. In FIG. 1, 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 μm, and the maximum particle size was 100 μm. 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 (φ200 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).
(b)アルカリエッチング処理
 上記で得られたアルミニウム板を水酸化ナトリウム濃度2.6質量%、アルミニウムイオン濃度6.5質量%、温度70℃の水溶液を用いてスプレーによるエッチング処理を行い、アルミニウム板を10g/m溶解した。その後、スプレーによる水洗を行った。
(B) Alkaline etching treatment The aluminum plate obtained above was subjected to etching treatment by spraying using an aqueous solution having a sodium hydroxide concentration of 2.6% by mass, an aluminum ion concentration of 6.5% by mass, and a temperature of 70 ° C. to obtain an aluminum plate. Was dissolved at 10 g / m 2 . Then, washing with water was performed by spraying.
(c)デスマット処理
 温度30℃の硝酸濃度1質量%水溶液(アルミニウムイオンを0.5質量%含む。)で、スプレーによるデスマット処理を行い、その後、スプレーで水洗した。デスマット処理に用いた硝酸水溶液は、硝酸水溶液中で交流を用いて電気化学的粗面化処理を行う工程の廃液を用いた。
(C) Desmutting treatment 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.
(d)電気化学的粗面化処理
 60Hzの交流電圧を用いて連続的に電気化学的粗面化処理を行った。このときの電解液は、硝酸10.5g/L水溶液(アルミニウムイオンを5g/L、アンモニウムイオンを0.007質量%含む。)、液温50℃であった。交流電源波形は図2に示した波形であり、電流値がゼロからピークに達するまでの時間TPが0.8msec、duty比1:1、台形の矩形波交流を用いて、カーボン電極を対極として電気化学的な粗面化処理を行った。補助アノードにはフェライトを用いた。使用した電解槽は図3に示すものを使用した。
 電流密度は電流のピーク値で30A/dm、電気量はアルミニウム板が陽極時の電気量の総和で220C/dmであった。補助陽極には電源から流れる電流の5%を分流させた。その後、スプレーによる水洗を行った。
(D) Electrochemical surface roughening treatment 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 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)アルカリエッチング処理
 アルミニウム板をカセイソーダ濃度26質量%、アルミニウムイオン濃度6.5質量%の水溶液を用いてスプレーによるエッチング処理を32℃で行い、アルミニウム板を0.50g/m溶解し、前段の交流を用いて電気化学的粗面化処理を行ったときに生成した水酸化アルミニウムを主体とするスマット成分を除去し、また、生成したピットのエッジ部分を溶解してエッジ部分を滑らかにした。その後、スプレーによる水洗を行った。
(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.
(f)デスマット処理
 温度30℃の硝酸濃度15質量%水溶液(アルミニウムイオンを4.5質量%含む。)で、スプレーによるデスマット処理を行い、その後、スプレーで水洗した。デスマットに用いた硝酸水溶液は、硝酸水溶液中で交流を用いて電気化学的粗面化処理を行う工程の廃液を用いた。
(F) Desmutting treatment 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. As the 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.
(g)電気化学的粗面化処理
 60Hzの交流電圧を用いて連続的に電気化学的粗面化処理を行った。このときの電解液は、塩酸5.0g/L水溶液(アルミニウムイオンを5g/L含む。)、温度35℃であった。交流電源波形は図2に示した形波であり、電流値がゼロからピークに達するまでの時間TPが0.8msec、duty比1:1、台形の炬形波交流を用いて、カーボン電極を対極として電気化学的粗面化処理を行った。補助アノードにはフェライトを用いた。使用した電解槽は図3に示すものを使用した。
 電流密度は電流のピーク値で25A/dm、電気量はアルミニウム板が陽極時の電気量の総和で50C/dmであった。その後、スプレーによる水洗を行った。
(G) Electrochemical surface roughening treatment 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)アルカリエッチング処理
 アルミニウム板をカセイソーダ濃度26質量%、アルミニウムイオン濃度6.5質量%の水溶液を用いてスプレーによるエッチング処理を32℃で行い、アルミニウム板を0.10g/m溶解し、前段の交流を用いて電気化学的粗面化処理を行ったときに生成した水酸化アルミニウムを主体とするスマット成分を除去し、また、生成したピットのエッジ部分を溶解してエッジ部分を滑らかにした。その後、スプレーによる水洗を行った。
(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 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.
(i)デスマット処理
 温度60℃の硫酸濃度25質量%水溶液(アルミニウムイオンを0.5質量%含む。)で、スプレーによるデスマット処理を行い、その後、スプレーによる水洗を行った。
(I) Desmutting treatment 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.
(j)陽極酸化処理
 図4に示す構造の陽極酸化装置(第一及び第二電解部長各6m、第一及び第二給電部長各3m、第一及び第二給電電極長各2.4m)を用いて陽極酸化処理を行った。第一及び第二電解部に供給した電解液としては、硫酸を用いた。電解液は、いずれも、硫酸濃度50g/L(アルミニウムイオンを0.5質量%含む。)、温度20℃であった。その後、スプレーによる水洗を行った。
 上記陽極酸化装置においては、電源67a及び電源67bからの電流は、第一給電部62aに設けられた第一給電電極65aに流れ、電解液を介してアルミニウム板11に流れ、第一電解部63aでアルミニウム板11表面に陽極酸化皮膜を生成させ、第一電解部63aに設けられた電解電極66a及び66bを通り、電極67a及び67bに戻る。
 電源67a及び67bから第一給電部62aに給電される電気量と、電源67c及び67dから第二給電部62bに給電される電気量とは等しく、また、第一電解部63a及び第二電解部63bにおける電流密度はともに約30A/dmであった。第二給電部62bでは、第一電解部63aで生成した1.35g/mの酸化皮膜面を通じて給電したことになる。最終的な酸化皮膜量は2.7g/mであった。
(J) Anodizing treatment The anodizing device having the structure shown in FIG. 4 (first and second electrolysis section lengths of 6 m each, first and second feeding section lengths of 3 m, and first and second feeding electrode lengths of 2.4 m) was used. Was used to perform anodizing treatment. Sulfuric acid was used as the electrolytic solution supplied to the first and second electrolysis sections. Each of the electrolytic solutions had a sulfuric acid concentration of 50 g / L (containing 0.5% by mass of aluminum ion) and a temperature of 20 ° C. Then, washing with water was performed by spraying.
In 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 . In the second power feeding portion 62b, 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)アルカリ金属ケイ酸塩処理
 陽極酸化処理により得られたアルミニウム支持体を温度30℃の3号ケイ酸ソーダの1質量%水溶液の処理槽中へ、10秒間、浸せきすることでアルカリ金属ケイ酸塩処理(シリケート処理)を行った。その後、井水を用いたスプレーによる水洗を行い、表面シリケート親水化処理された支持体を得た。上記のようにして得られたアルカリ金属珪酸塩処理後のアルミニウム支持体上に、下記組成の下塗り液を塗布し、80℃で15秒間乾燥し、塗膜を形成させた。乾燥後の塗膜の被覆量は15mg/mであった。
(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 .
-下塗り液組成-
・下記化合物:0.3部
・メタノール:100部
・水:1部
-Undercoat composition-
・ The following compounds: 0.3 parts ・ Methanol: 100 parts ・ Water: 1 part
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
 なお、Etはエチル基を表す。 Note that Et represents an ethyl group.
(実施例1-1~13-1、並びに、比較例1-1及び2-1)
<画像記録層(重層)の形成>
 得られたウェブ状の基板に下記組成の下層用塗布液を塗布量が0.85g/mになるようバーコーターで塗布したのち160℃で44秒間乾燥し、直ちに17℃~20℃の冷風で支持体の温度が35℃になるまで冷却した。
 その後、下記組成の上層用塗布液を塗布量が0.22g/mになるようバーコーター塗布したのち、148℃で25秒間乾燥し、更に20℃~26℃の風で徐冷し、実施例及び比較例の各平版印刷版原版を作製した。
(Examples 1-1 to 13-1 and Comparative Examples 1-1 and 2-1)
<Formation of image recording layer (multilayer)>
The web-shaped substrate thus obtained was coated with a lower layer coating solution having the following composition by a bar coater so that the coating amount was 0.85 g / m 2 , followed by drying at 160 ° C. for 44 seconds and immediately cooling with cold air at 17 ° C.-20 ° C. It was cooled until the temperature of the support reached 35 ° C.
Then, a coating solution for the upper layer having the following composition was applied by a bar coater to a coating amount of 0.22 g / m 2 , dried at 148 ° C. for 25 seconds, and then gradually cooled by a wind at 20 ° C. to 26 ° C. The lithographic printing plate precursors of Examples and Comparative Examples were produced.
<下層用塗布液>
・表1に記載のアルカリ可溶性樹脂:表1に記載の添加量(例えば、実施例1-1では1.92部となる。)
・ノボラック樹脂:0.192部
・シアニン染料A:0.134部
・4,4’-ビスヒドロキシフェニルスルホン:0.126部
・無水テトラヒドロフタル酸:0.190部
・p-トルエンスルホン酸:0.008部
・3-メトキシ-4-ジアゾフェニルアミンヘキサフルオロホスフェート:0.032部
・エチルバイオレットの対イオンを6-ヒドロキシナフタレンスルホン酸に変えたもの:0.0781部
・ポリマー1(下記に示すポリマー):0.035部
・メチルエチルケトン:25.41部
・1-メトキシ-2-プロパノール:12.97部
・γ-ブチロラクトン:13.18部
<Coating liquid for lower layer>
-Alkali-soluble resin described in Table 1: The addition amount described in Table 1 (for example, it is 1.92 parts in Example 1-1).
・ Novolak resin: 0.192 part ・ Cyanine dye A: 0.134 part ・ 4,4'-bishydroxyphenyl sulfone: 0.126 part ・ Tetrahydrophthalic anhydride: 0.190 part ・ p-toluenesulfonic acid: 0 0.008 part 3-methoxy-4-diazophenylamine hexafluorophosphate: 0.032 part-Ethyl violet counter ion changed to 6-hydroxynaphthalenesulfonic acid: 0.0781 part-Polymer 1 (shown below Polymer): 0.035 parts, methyl ethyl ketone: 25.41 parts, 1-methoxy-2-propanol: 12.97 parts, γ-butyrolactone: 13.18 parts
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
<上層用塗布液>
・m,p-クレゾールノボラック樹脂(m/p比=6/4、重量平均分子量4,500、未反応クレゾール0.8質量%含有):0.3479部
・ポリマー3(下記に示すポリマー):0.1403部
・表1に記載の特定高分子化赤外線吸収剤:表1に記載の添加量(例えば、実施例1-1では0.5部となる。)
・ポリマー1:0.015部
・ポリマー2(下記に示すポリマー):0.00328部
・表1に記載のカチオン及びアニオンからなるオニウム塩化合物:表1に記載の添加量(例えば、実施例1-1では0.08部となる。)
・界面活性剤(メガファックF-780F、DIC(株)製:0.008部
・メチルエチルケトン:6.79部
・1-メトキシ-2-プロパノール:13.07部
<Upper layer coating liquid>
M, p-cresol novolac resin (m / p ratio = 6/4, weight average molecular weight 4,500, containing 0.8% by mass of unreacted cresol): 0.3479 parts Polymer 3 (polymer shown below): 0.1403 parts-Specific polymerized infrared absorbent described in Table 1: Addition amount described in Table 1 (for example, 0.5 parts in Example 1-1).
Polymer 1: 0.015 part Polymer 2 (polymer shown below): 0.00328 part Onium salt compound consisting of cation and anion described in Table 1: Addition amount described in Table 1 (for example, Example 1 -1 is 0.08 copies.)
-Surfactant (Megafac F-780F, manufactured by DIC Corporation: 0.008 parts) -Methyl ethyl ketone: 6.79 parts-1-Methoxy-2-propanol: 13.07 parts
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
(実施例1-2~実施例13-2並びに比較例1-2及び2-2)
 実施例1-1と同様にして得られた支持体上に、下記組成の単層用塗布液を塗布量が1.2g/mとなるよう塗布、乾燥して記録層を形成し、実施例1-2~実施例13-2並びに比較例1-2及び2-2の平版印刷版原版を得た。
(Example 1-2 to Example 13-2 and Comparative Examples 1-2 and 2-2)
On the support obtained in the same manner as in Example 1-1, a single-layer coating solution having the following composition was applied to give a coating amount of 1.2 g / m 2, and dried to form a recording layer. The lithographic printing plate precursors of Example 1-2 to Example 13-2 and Comparative Examples 1-2 and 2-2 were obtained.
<単層用塗布液>
・表2に記載のアルカリ可溶性樹脂:2.625部
・m,p-クレゾールノボラック樹脂:0.525部
・表2に記載の特定高分子化赤外線吸収剤:表2に記載の添加量:0.15部
・4,4’-ビスヒドロキシフェニルスルホン:0.225部
・無水テトラヒドロフタル酸:0.3部
・p-トルエンスルホン酸:0.015部
・3-メトキシ-4-ジアゾフェニルアミンヘキサフルオロホスフェート:0.045部
・エチルバイオレットの対イオンを6-ヒドロキシナフタレンスルホン酸に変えたもの:0.1125部
・界面活性剤(メガファックF-780F,DIC(株)製):0.0525部
・メチルエチルケトン:22.5部
・1-メトキシ-2-プロパノール:11.25部
・γ-ブチロラクトン:11.25部
・表2に記載のカチオン及びアニオンからなるオニウム塩化合物:0.516部
<Single layer coating liquid>
-Alkali-soluble resin shown in Table 2: 2.625 parts-m, p-cresol novolac resin: 0.525 part-Specific polymerized infrared absorber shown in Table 2: Addition amount shown in Table-2: 0 .15 parts 4,4'-bishydroxyphenyl sulfone: 0.225 part tetrahydrophthalic anhydride: 0.3 part p-toluenesulfonic acid: 0.015 part 3-methoxy-4-diazophenylamine hexa Fluorophosphate: 0.045 parts-Ethyl violet counter ion changed to 6-hydroxynaphthalene sulfonic acid: 0.1125 parts-Surfactant (Megafuck F-780F, manufactured by DIC Corporation): 0.0525 Parts Methyl ethyl ketone: 22.5 parts 1-methoxy-2-propanol: 11.25 parts γ-butyrolactone: 11.25 parts Onium salt compound consisting of one and the anion: 0.516 parts
<平版印刷版原版の評価>
-露光-
 実施例及び比較例の平版印刷版原版を、Creo社製Trendsetterにて露光エネルギーを変えて、テストパターンを画像状に描き込みを行った。
<Evaluation of original planographic printing plate>
-exposure-
The lithographic printing plate precursors of Examples and Comparative Examples were changed in exposure energy with a Trendsetter manufactured by Creo, and a test pattern was drawn in an image.
-現像処理-
 その後、実施例及び比較例の平版印刷版原版について、富士フイルム(株)製現像液XP-D(希釈して、電導度43mS/cmとしたもの)を仕込んだ富士フイルム(株)製PSプロセッサーLP940Hを用い、現像温度30℃、現像時間12秒で現像を行った。
-Development processing-
After that, with regard to the planographic printing plate precursors of Examples and Comparative Examples, a PS processor manufactured by FUJIFILM Co., Ltd. charged with a developer XP-D manufactured by FUJIFILM Corporation (diluted to have an electric conductivity of 43 mS / cm) Development was carried out using LP940H at a development temperature of 30 ° C. and a development time of 12 seconds.
-現像ラチチュード評価-
 上記の現像処理において、現像液の希釈率を変えて電導度を調整して現像処理を行い、画像部が溶出されず、かつ、現像不良の感光層残膜に起因する汚れ及び着色がなく良好に現像が行えた現像液において、電導度の最大値と、電導度の最小値との差(mS/cm)(以下、「電導度差異」ともいう。)を現像ラチチュードとして、下記の評価基準に従い評価を行った。評価点数が高いほど現像ラチチュードに優れ、評価点数が3以上であれば現像ラチチュードにより優れるといえる。
(評価基準)
 5  :電導度差異(mS/cm)が7以上である。
 4.5:電導度差異(mS/cm)が6以上7未満である。
 4  :電導度差異(mS/cm)が5以上6未満である。
 3.5:電導度差異(mS/cm)が4以上5未満である。
 3  :電導度差異(mS/cm)が3以上4未満である。
 2.5:電導度差異(mS/cm)が2以上3未満である。
 2  :電導度差異(mS/cm)が1以上2未満である。
 1.5:電導度差異(mS/cm)が1未満である。
 1  :現像不可
-Development latitude evaluation-
In the above-mentioned development processing, the development ratio is adjusted by changing the dilution ratio of the developing solution to adjust the conductivity, the image area is not eluted, and there is no stain or coloration due to the poorly developed photosensitive layer residual film. In the developing solution which has been developed, the difference (mS / cm) between the maximum value of conductivity and the minimum value of conductivity (hereinafter, also referred to as “conductivity difference”) is used as the development latitude, and the following evaluation criteria are used. The evaluation was performed according to. It can be said that the higher the evaluation score, the better the development latitude, and the evaluation score of 3 or more, the better the development latitude.
(Evaluation criteria)
5: The difference in conductivity (mS / cm) is 7 or more.
4.5: The difference in conductivity (mS / cm) is 6 or more and less than 7.
4: The difference in conductivity (mS / cm) is 5 or more and less than 6.
3.5: The difference in conductivity (mS / cm) is 4 or more and less than 5.
3: The difference in conductivity (mS / cm) is 3 or more and less than 4.
2.5: The difference in conductivity (mS / cm) is 2 or more and less than 3.
2: The difference in conductivity (mS / cm) is 1 or more and less than 2.
1.5: The difference in conductivity (mS / cm) is less than 1.
1: Not developable
-耐キズ性評価-
 得られた平版印刷版原版を25℃60%RHの環境下で2時間調湿後、2.5cm×2.5cmに打ち抜き、新東科学(株)製の連続加重式引掻強度試験機TYPE-18に取り付け、打ち抜いていない平版印刷版原版の表面の上に、打ち抜いた平版印刷版原版の裏面が接触するようにセットし、0gf~1,500gf(0N~14.7N)の圧力で平版印刷版原版の数箇所に擦れ傷をつけた。擦れ傷をつけた平版印刷版原版をCreo社製Trendsetter3244にセットし、解像度2,400dpi(dot per inch、1inchは2.54cm)で出力7W、外面ドラム回転数150rpm(revolutions per minute)、版面エネルギー110mJ/cmで画像露光した。
 画像露光後の平版印刷版原版を、(株)東京機械製作所製オフセット輪転印刷機に装着し、新聞用印刷インキとしてインクテック(株)製ソイビーKKST-S(紅)、湿し水としてサカタインクス(株)製エコセブンN-1を用い、新聞用紙に100,000枚/時のスピードで印刷した。印刷過程において、1,000枚目の印刷物をサンプリングし、擦れ傷に起因するキズ汚れの程度を目視で観察した。
 耐キズ性の評価は1~5の官能評価で行い、3以上が実用上好ましいレベルである。
(評価基準)
5  :画像部に視認可能なキズ汚れが見られない。
4.5:視認では確認はできないが、画像部に25倍率のルーペで確認可能なキズ汚れが1か所見られる。
4  :視認では確認はできないが、画像部に6倍率のルーペで確認可能なキズ汚れが1か所見られる。
3  :視認では確認はできないが、画像部に6倍率のルーペで確認可能なキズ汚れが2か所以上5か所以下見られる。
2  :画像部の複数個所に視認で確認可能なキズ汚れが見られる。
1  :画像部全面に視認可能なキズ汚れが見られる。
-Scratch resistance evaluation-
The lithographic printing plate precursor thus obtained was conditioned for 2 hours in an environment of 25 ° C. and 60% RH, punched out into 2.5 cm × 2.5 cm, and manufactured by Shinto Kagaku Co., Ltd. as a continuous load type scratch strength tester TYPE. Mounted on -18, set so that the back surface of the punched lithographic printing plate precursor comes into contact with the front surface of the lithographic printing plate precursor that has not been punched out, and lithographically plate it at a pressure of 0 gf to 1,500 gf (0N to 14.7N). Several parts of the printing plate precursor were scratched and scratched. The lithographic printing plate precursor with scratches was set on the Trendsetter 3244 manufactured by Creo, and the output was 7 W at the resolution of 2,400 dpi (dot per inch, 1 inch was 2.54 cm), the outer surface drum rotation speed was 150 rpm (revolutions per minute), and the plate surface energy was set. Image exposure was performed at 110 mJ / cm 2 .
The lithographic printing plate precursor after image exposure was mounted on an offset rotary printing machine manufactured by Tokyo Kikai Seisakusho, and Soybee KKST-S (red) manufactured by Inktec Co., Ltd. was used as printing ink for newspapers, and Sakata Inx as dampening water ( Using Eco Seven N-1 manufactured by Co., Ltd., printing was performed on newsprint paper at a speed of 100,000 sheets / hour. In the printing process, the 1,000th printed material was sampled, and the degree of scratch stains caused by scratches was visually observed.
The scratch resistance is evaluated by a sensory evaluation of 1 to 5, and 3 or more is a practically preferable level.
(Evaluation criteria)
5: No visible scratch stain is seen in the image area.
4.5: Although it cannot be visually confirmed, there is one scratch stain in the image area that can be confirmed with a magnifying glass of 25 magnifications.
4: Although it cannot be visually confirmed, there is one scratch on the image area that can be confirmed with a magnifying glass of 6 magnifications.
3: Although it cannot be visually confirmed, there are two or more and five or less scratches and stains in the image area that can be confirmed with a magnifying glass of 6 magnifications.
2: Scratch stains that can be visually confirmed are found at multiple locations in the image area.
1: Visual stains are visible on the entire surface of the image area.
-処理安定性評価-
 露光工程において、175lpi(lines per inch)/2400dpiの網点面積率1%~99%のFMスクリーンチャートが入ったテストパタ-ンを画像状に描き込み(露光)を行った。実施例及び比較例の平版印刷版原版について、富士フイルム(株)製現像液XP-D(希釈して、電導度43mS/cmとしたもの、pH13.1)を仕込んだ富士フイルム(株)製PSプロセッサーLP940Hを用い、現像温度30℃、現像時間12秒で現像を行った。現像処理の進行に伴い、富士フイルム(株)製現像補充液XP-DRを用いて、自動補充システムによる現像液の補充を行った。
 下記の処理条件で7日間連続処理を行い、版上のFMスクリーン50%網点の網点面積率(%)を、X-RITE社製iCPlate2を用いて測定し、連続処理中の50%網点の網点面積率(%)の最大値と最小値の差異(以下、単に「50%網点再現の差異」ともいう。)を求め、下記評価基準に従って評価を行った。
 評価点数が高いほど50%網点再現の差異が小さく、処理安定性が良好であることを示し、評価点数が3以上であると実用上好ましいレベルといえる。
<<処理条件>>
 現像温度 30℃
 現像時間 12秒
 現像槽容量 20L
 版材搬送速度 1,400mm/分
 補充液希釈率 現像補充液XP-DR:水=1:6.5
 稼働時経時補充量 50mL/時
 停止時経時補充量 15mL/時
 処理補充量 20mL/m
<<処理パターン>>
月曜日~水曜日:露光済み平版印刷版(版材)(0.8m)を26枚/日の現像処理を行った。
木曜日:露光済み平版印刷版(版材)(0.8m)を84枚/日の現像処理を行った。
金曜日:露光済み平版印刷版(版材)(0.8m)を14枚/日の現像処理を行った。
(評価基準)
 5  :50%網点再現の差異が5%未満である。
 4.5:50%網点再現の差異が5%以上5.5%未満である。
 4  :50%網点再現の差異が5.5%以上6%未満である。
 3.5:50%網点再現の差異が6%以上6.5%未満である。
 3  :50%網点再現の差異が6.5%以上7%未満である。
 2  :50%網点再現の差異が7%以上である。
 1  :50%網点再現の差異が8%以上である。
-Processing stability evaluation-
In the exposure step, a test pattern containing an FM screen chart of 175 lpi (lines per inch) / 2400 dpi with a dot area ratio of 1% to 99% was imagewise drawn (exposed). The lithographic printing plate precursors of Examples and Comparative Examples were manufactured by Fuji Film Co., Ltd., which was prepared by using Developer XP-D developer (diluted to have an electric conductivity of 43 mS / cm, pH 13.1). Development was performed using a PS processor LP940H at a development temperature of 30 ° C. and a development time of 12 seconds. As the development process progressed, the developer replenisher XP-DR manufactured by FUJIFILM Corporation was used to replenish the developer with an automatic replenishment system.
After continuous treatment for 7 days under the following treatment conditions, the halftone dot area ratio (%) of the FM screen 50% halftone dots on the plate was measured using iCPlate2 manufactured by X-RITE, and 50% halftone dots during continuous treatment were measured. The difference between the maximum value and the minimum value of the dot area ratio (%) of the dots (hereinafter, also simply referred to as “difference in 50% dot reproduction”) was obtained and evaluated according to the following evaluation criteria.
The higher the evaluation score is, the smaller the difference of 50% halftone dot reproduction is, and the better the processing stability is. The evaluation score of 3 or more is considered to be a practically preferable level.
<< processing conditions >>
Development temperature 30 ℃
Development time 12 seconds Development tank capacity 20L
Plate material conveying speed 1,400 mm / min Replenisher dilution ratio Development replenisher XP-DR: Water = 1: 6.5
Replenishment amount with time during operation 50 mL / hour Replenishment amount with time during stoppage 15 mL / hour Treatment replenishment amount 20 mL / m 2
<< Processing pattern >>
Monday-Wednesday: The exposed lithographic printing plate (plate material) (0.8 m 2 ) was developed at 26 sheets / day.
Thursday: The exposed lithographic printing plate (plate material) (0.8 m 2 ) was developed at 84 sheets / day.
Friday: The exposed lithographic printing plate (plate material) (0.8 m 2 ) was developed at 14 sheets / day.
(Evaluation criteria)
5: 50% Difference in halftone dot reproduction is less than 5%.
4.5: 50% Difference in halftone dot reproduction is 5% or more and less than 5.5%.
4: 50% difference in dot reproduction is 5.5% or more and less than 6%.
3.5: 50% Difference in halftone dot reproduction is 6% or more and less than 6.5%.
3: 50% Difference in halftone dot reproduction is 6.5% or more and less than 7%.
2: 50% Difference in dot reproduction is 7% or more.
1: 50% difference in dot reproduction is 8% or more.
-現像カス(シリケートカス)抑制性評価-
 30cm×65cmの大きさにカットした平版印刷版原版を用いて、上記処理安定性評価における現像処理条件で60版処理した後に、処理した平版印刷版の画像部を目視で観察し、現像液内の不溶物に起因すると思われる傷の有無を目視で観察し、現像カス抑制性の評価を行った。
-Development residue (silicate residue) inhibition evaluation-
Using a lithographic printing plate precursor cut into a size of 30 cm × 65 cm, 60-plate processing was carried out under the development processing conditions in the above processing stability evaluation, and then the image area of the processed lithographic printing plate was visually observed, The presence or absence of scratches, which are considered to be caused by the insoluble matter, was visually observed to evaluate the development residue suppressing property.
Figure JPOXMLDOC01-appb-T000027
Figure JPOXMLDOC01-appb-T000027
Figure JPOXMLDOC01-appb-T000028
Figure JPOXMLDOC01-appb-T000028
 表1及び表2における構成単位aは、上記式1で表される構成単位を表し、構成単位bは上記側鎖にフェノール性水酸基を有する構成単位を表す。
 また、表1及び表2に記載のアルカリ可溶性樹脂の組成比(mol比)は、表1及び表2の左に記載の構成単位から順に記載したものであり、例えば、実施例1-1では、a-1が28モル%、b-1が26モル%、c-1が20モル%、c-2が6モル%、及び、c-3が20モル%である。
 更に、表1及び表2に記載の各略号の詳細を、以下に示す。
 a-1:下記に示す構成単位
The structural unit a in Table 1 and Table 2 represents the structural unit represented by the above formula 1, and the structural unit b represents the structural unit having a phenolic hydroxyl group in the side chain.
The composition ratios (mol ratios) of the alkali-soluble resins shown in Tables 1 and 2 are listed in order from the structural units shown on the left of Tables 1 and 2, and, for example, in Example 1-1. A-1 is 28 mol%, b-1 is 26 mol%, c-1 is 20 mol%, c-2 is 6 mol%, and c-3 is 20 mol%.
Further, details of each abbreviation shown in Table 1 and Table 2 are shown below.
a-1: Structural unit shown below
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000029
 b-1:下記に示す構成単位 B-1: Structural units shown below
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000030
 c-1~c-3:下記に示す構成単位 C-1 to c-3: Structural units shown below
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000031
<<特定IR色素(1)>>
 特定IR色素(1)の合成に使用されるアルカリ可溶性樹脂は、下記に示す構造式IIで表される構成単位を含むレゾール樹脂:RM-1(Lekai 社製、m-クレゾール樹脂のメチロール化物)を用いた。上記RM-1:100gをN,N-ジメチルホルムアミド400mLに溶解して溶液を調製し、40℃で、0.2gの水酸化ナトリウムをゆっくりと溶液に添加し、得られた反応物を30分間撹拌した。N,N-ジメチルホルムアミド100mLに溶解した2-[2-[2-クロロ-3-[2-(1,3-ジヒドロ-1,1,3-トリメチル-2H-)フェニル-フルオレン-2-フォーク)-アセタール]-1-シクロペンテン-1-イル-エテン]-1,1,3-トリメチル-1H-フェニルインドールテトラメチルベンゼンスルホネート酸塩溶液(シアニン染料)を、RM-1が溶解した溶液にゆっくりと添加し、反応を10時間行った。次いで、溶液を室温で冷却し、生成物を水中で沈降させることにより分離した。得られた生成物は真空濾過によって回収し、水ですすいだ後、空気中で乾燥させた後で、特定IR色素(1)が得られた。
<< Specific IR Dye (1) >>
The alkali-soluble resin used in the synthesis of the specific IR dye (1) is a resole resin containing a constitutional unit represented by the structural formula II shown below: RM-1 (manufactured by Lekai, methylol compound of m-cresol resin). Was used. A solution was prepared by dissolving 100 g of the above RM-1 in 400 mL of N, N-dimethylformamide, and at 40 ° C., 0.2 g of sodium hydroxide was slowly added to the solution, and the obtained reaction product was added for 30 minutes. It was stirred. 2- [2- [2-chloro-3- [2- (1,3-dihydro-1,1,3-trimethyl-2H-) phenyl-fluorene-2-fork dissolved in 100 mL of N, N-dimethylformamide ) -Acetal] -1-cyclopenten-1-yl-ethene] -1,1,3-trimethyl-1H-phenylindole tetramethylbenzenesulfonate solution (cyanine dye) is slowly added to the solution in which RM-1 is dissolved. Was added and the reaction was carried out for 10 hours. The solution was then cooled at room temperature and the product separated by settling in water. The resulting product was collected by vacuum filtration, rinsed with water and dried in air to give the specific IR dye (1).
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000032
 上記構造式II中、Rは、炭素数1~12の炭化水素基、アルコキシ基、アリール基、ハロゲン原子を表し、m及びnは、それぞれ独立に1~12の整数を表す。 In the above structural formula II, R represents a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryl group, or a halogen atom, and m and n each independently represent an integer of 1 to 12.
<<特定IR色素(2)>>
 特定IR色素(2)の合成に用いられるアルカリ可溶性樹脂は、既述の構造式I-1に示される化合物:BTB-29(威海天城化学工業(株)製、m-クレゾール樹脂のメチロール化物)を用いた。BTB-29をN,N-ジメチルホルムアミド400mLに溶解して溶液を調製した。40℃で、0.2gの水酸化ナトリウムをゆっくりと溶液に添加し、反応物を30分間撹拌した。
 N,N-ジメチルホルムアミド100mLに溶解した2-[2-[2-クロロ-3-[2-(1,3-ジヒドロ-1,1,3-トリメチル-2H-)フェニル-フルオレン-2-フォーク)-アセタール]-1-シクロペンテン-1-イル-エテン]-1,1,3-トリメチル-1H-フェニルインドールテトラメチルベンゼンスルホネート酸塩溶液(シアニン染料)を、BTB-29が溶解された溶液にゆっくりと添加し、反応を10時間行った。次いで、溶液を室温で冷却し、生成物を水中で沈降させることにより分離する。生成物を真空濾過によって回収し、水ですすいだ後で空気中で乾燥させることで、特定IR色素(2)が得られた。
<< Specific IR Dye (2) >>
The alkali-soluble resin used for the synthesis of the specific IR dye (2) is a compound represented by the above-mentioned structural formula I-1: BTB-29 (a methylol compound of m-cresol resin manufactured by Weihai Amagi Chemical Co., Ltd.). Was used. A solution was prepared by dissolving BTB-29 in 400 mL of N, N-dimethylformamide. At 40 ° C., 0.2 g sodium hydroxide was slowly added to the solution and the reaction was stirred for 30 minutes.
2- [2- [2-chloro-3- [2- (1,3-dihydro-1,1,3-trimethyl-2H-) phenyl-fluorene-2-fork dissolved in 100 mL of N, N-dimethylformamide ) -Acetal] -1-cyclopenten-1-yl-ethene] -1,1,3-trimethyl-1H-phenylindole tetramethylbenzenesulfonate solution (cyanine dye) to a solution in which BTB-29 is dissolved. It was added slowly and the reaction was run for 10 hours. The solution is then cooled at room temperature and the product is separated by settling in water. The product was collected by vacuum filtration, rinsed with water and dried in air to give the specific IR dye (2).
 シアニン色素A:下記化合物 Cyanine dye A: the following compound
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000033
 ca-1及びca-11:下記カチオン Ca-1 and ca-11: the following cations
Figure JPOXMLDOC01-appb-C000034
Figure JPOXMLDOC01-appb-C000034
cb-1:下記カチオン cb-1: the following cation
Figure JPOXMLDOC01-appb-C000035
Figure JPOXMLDOC01-appb-C000035
 an-1:下記アニオン An-1: the following anion
Figure JPOXMLDOC01-appb-C000036
Figure JPOXMLDOC01-appb-C000036
 なお、実施例1-5、1-6、2-5及び2-6の平版印刷版原版については、富士フイルム(株)製現像液DP-4(ケイ酸塩含有)を、水道水で9倍希釈したものを仕込んだ富士フイルム(株)製PSプロセッサーLP940Hを用い、現像温度を28℃に保ち、現像時間25秒で現像を行った。 For the planographic printing plate precursors of Examples 1-5, 1-6, 2-5 and 2-6, the developer DP-4 (containing silicate) manufactured by Fuji Film Co., Ltd. Development was carried out at a development time of 25 seconds using a PS processor LP940H manufactured by FUJIFILM Corporation, which was prepared by doubling the dilution.
 表1及び表2に記載した結果から、本開示に係る平版印刷版原版である実施例の平版印刷版原版は、比較例の平版印刷版原版に比べて、現像ラチチュード及び耐キズ性に優れた平版印刷版が得られることがわかる。
 また、本開示に係る平版印刷版原版である実施例の平版印刷版原版は、処理安定性にも優れた平版印刷版が得られることがわかる。
From the results shown in Table 1 and Table 2, the lithographic printing plate precursor of the example, which is the lithographic printing plate precursor according to the present disclosure, was excellent in development latitude and scratch resistance as compared with the lithographic printing plate precursor of Comparative Example. It can be seen that a lithographic printing plate can be obtained.
Further, it can be seen that the lithographic printing plate precursor of the example which is the lithographic printing plate precursor according to the present disclosure can provide a lithographic printing plate excellent in processing stability.
 2018年10月17日に出願された日本国特許出願第2018-196166号の開示は、その全体が参照により本明細書に取り込まれる。
 本明細書に記載された全ての文献、特許出願、及び、技術規格は、個々の文献、特許出願、及び、技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書中に参照により取り込まれる。
The disclosure of Japanese Patent Application No. 2018-196166 filed on Oct. 17, 2018 is incorporated herein by reference in its entirety.
All documents, patent applications, and technical standards mentioned in this specification are to the same extent as if each individual document, patent application, and technical standard were specifically and individually noted to be incorporated by reference. Are incorporated herein by reference.
1 アルミニウム板
2,4 ローラ状ブラシ
3 研磨スラリー液
5,6,7,8 支持ローラ
11 アルミニウムウエブ
12 ラジアルドラムローラ
13a,13b 主極
14 電解処理液
15a,15b 電解液供給口
16 スリット
17 電解液通路
18 補助陽極
19a,19b サイリスタ
20 交流電源
40,41 主電解槽
50,51 補助陽極槽
62a 第一給電部
62b 第二給電部
63a 第一電解部
63b 第二電解部
64a,64b 支持ローラ
65a 第一給電電極
65b 第二給電電極
66a,66b,66c,66d 電解電極
67a,67b,67c,67d 電源
I 電流値
Ip 電流のピーク
t 時間
TP 電流値がゼロからピークに達するまでの時間
1 Aluminum Plate 2, 4 Roller Brush 3 Polishing Slurry Liquid 5, 6, 7, 8 Support Roller 11 Aluminum Web 12 Radial Drum Rollers 13a, 13b Main Electrode 14 Electrolytic Treatment Liquids 15a, 15b Electrolyte Supply Port 16 Slit 17 Electrolyte Passage 18 Auxiliary anode 19a, 19b Thyristor 20 AC power supply 40, 41 Main electrolysis tank 50, 51 Auxiliary anode tank 62a First power feeding part 62b Second power feeding part 63a First electrolysis part 63b Second electrolysis part 64a, 64b Support roller 65a One feeding electrode 65b Second feeding electrodes 66a, 66b, 66c, 66d Electrolytic electrodes 67a, 67b, 67c, 67d Power source I Current value Ip Current peak t time TP Time until current value reaches zero peak

Claims (11)

  1.  支持体上に画像記録層を有し、
     前記画像記録層が、アルカリ可溶性樹脂、重量平均分子量4,000以上の赤外線吸収剤、及びオニウム塩化合物を含む、
     平版印刷版原版。
    Having an image recording layer on a support,
    The image recording layer contains an alkali-soluble resin, an infrared absorber having a weight average molecular weight of 4,000 or more, and an onium salt compound,
    Original planographic printing plate.
  2.  前記赤外線吸収剤が、酸性基を有する、請求項1に記載の平版印刷版原版。 The lithographic printing plate precursor according to claim 1, wherein the infrared absorber has an acidic group.
  3.  前記赤外線吸収剤が、赤外線を吸収する色素構造とポリマー構造とを含む、請求項1又は請求項2に記載の平版印刷版原版。 The lithographic printing plate precursor according to claim 1 or 2, wherein the infrared absorbing agent includes a dye structure that absorbs infrared rays and a polymer structure.
  4.  前記ポリマー構造が、フェノール樹脂構造を含む、請求項3に記載の平版印刷版原版。 The lithographic printing plate precursor according to claim 3, wherein the polymer structure includes a phenol resin structure.
  5.  前記画像記録層が、上層及び下層を有する、請求項1~請求項4のいずれか1項に記載の平版印刷版原版。 The lithographic printing plate precursor according to any one of claims 1 to 4, wherein the image recording layer has an upper layer and a lower layer.
  6.  前記オニウム塩化合物が、第4級アンモニウム塩化合物、及び、スルホニウム塩化合物よりなる群から選ばれる少なくとも1種の化合物である、請求項1~請求項5のいずれか1項に記載の平版印刷版原版。 The lithographic printing plate according to any one of claims 1 to 5, wherein the onium salt compound is at least one compound selected from the group consisting of a quaternary ammonium salt compound and a sulfonium salt compound. Original version.
  7.  前記アルカリ可溶性樹脂が、アセタール樹脂、フェノール樹脂、アクリル樹脂、及び、ウレア結合、ウレタン結合又はアミド結合を主鎖に有する樹脂よりなる群から選ばれる少なくとも1種の樹脂を含む、請求項1~請求項6のいずれか1項に記載の平版印刷版原版。 The alkali-soluble resin contains at least one resin selected from the group consisting of acetal resin, phenol resin, acrylic resin, and resin having urea bond, urethane bond or amide bond in the main chain. Item 10. The planographic printing plate precursor according to any one of items 6.
  8.  前記アルカリ可溶性樹脂が、下記式1で表される構成単位と、側鎖にフェノール性水酸基を有する構成単位と、を有する、請求項1~請求項7のいずれか1項に記載の平版印刷版原版。
    Figure JPOXMLDOC01-appb-C000001

     式1中、Rは、アルキル基又はアリール基を表す。
    The lithographic printing plate according to any one of claims 1 to 7, wherein the alkali-soluble resin has a structural unit represented by the following formula 1 and a structural unit having a phenolic hydroxyl group in a side chain. Original version.
    Figure JPOXMLDOC01-appb-C000001

    In Formula 1, R represents an alkyl group or an aryl group.
  9.  ノンシリケート現像用平版印刷版原版である、請求項1~請求項8のいずれか1項に記載の平版印刷版原版。 The lithographic printing plate precursor according to any one of claims 1 to 8, which is a lithographic printing plate precursor for non-silicate development.
  10.  請求項1~請求項9のいずれか1項に記載の平版印刷版原版を赤外線レーザーを用いて画像様に露光する工程と、
     シリケート化合物を含まないpH9以上のアルカリ現像液を用いて現像する工程と、
    を含む、平版印刷版の作製方法。
    A step of imagewise exposing the lithographic printing plate precursor according to any one of claims 1 to 9 using an infrared laser;
    Developing with an alkali developer having a pH of 9 or higher containing no silicate compound,
    A method for producing a lithographic printing plate, comprising:
  11.  前記アルカリ現像液の液活性を、前記アルカリ現像液の電導度で測定し、測定された測定値に従って補充液を加えて目標の電導度となるように調整し、液活性を制御する工程を含む、請求項10に記載の平版印刷版の作製方法。 The step of controlling the liquid activity of the alkaline developer by measuring the conductivity of the alkaline developer, adjusting the conductivity by adding a replenisher according to the measured value, and adjusting it to the target conductivity. The method for producing a lithographic printing plate according to claim 10.
PCT/JP2019/040523 2018-10-17 2019-10-15 Lithographic printing original plate and lithographic printing plate production method WO2020080371A1 (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002169300A (en) * 2000-11-30 2002-06-14 Fuji Photo Film Co Ltd Method for forming image on lithographic printing plate
JP2003012746A (en) * 2001-06-26 2003-01-15 Fuji Photo Film Co Ltd Image recording material and polymer compound used therefor
JP2003103950A (en) * 2001-09-28 2003-04-09 Fuji Photo Film Co Ltd Lithographic printing original plate
JP2006267746A (en) * 2005-03-24 2006-10-05 Fuji Photo Film Co Ltd Positive image forming material
WO2018061708A1 (en) * 2016-09-29 2018-04-05 富士フイルム株式会社 Positive planographic printing original plate and method for manufacturing same, and method for producing planographic printing plate

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002169300A (en) * 2000-11-30 2002-06-14 Fuji Photo Film Co Ltd Method for forming image on lithographic printing plate
JP2003012746A (en) * 2001-06-26 2003-01-15 Fuji Photo Film Co Ltd Image recording material and polymer compound used therefor
JP2003103950A (en) * 2001-09-28 2003-04-09 Fuji Photo Film Co Ltd Lithographic printing original plate
JP2006267746A (en) * 2005-03-24 2006-10-05 Fuji Photo Film Co Ltd Positive image forming material
WO2018061708A1 (en) * 2016-09-29 2018-04-05 富士フイルム株式会社 Positive planographic printing original plate and method for manufacturing same, and method for producing planographic printing plate

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