EP1690685B1 - Précurseur de plaque d'impression planographique - Google Patents

Précurseur de plaque d'impression planographique Download PDF

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Publication number
EP1690685B1
EP1690685B1 EP06002128A EP06002128A EP1690685B1 EP 1690685 B1 EP1690685 B1 EP 1690685B1 EP 06002128 A EP06002128 A EP 06002128A EP 06002128 A EP06002128 A EP 06002128A EP 1690685 B1 EP1690685 B1 EP 1690685B1
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EP
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Prior art keywords
acid
group
printing plate
planographic printing
plate precursor
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EP06002128A
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German (de)
English (en)
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EP1690685A2 (fr
EP1690685A3 (fr
Inventor
Yusuke c/o Fuji Photo Film Co. Ltd. Hatanaka
Kotaro c/o Fuji Photo Film Co. Ltd. Watanabe
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Fujifilm Corp
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Fujifilm Corp
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C1/00—Forme preparation
    • B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
    • B41C1/1008—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C1/00—Forme preparation
    • B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
    • B41C1/1008—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials
    • B41C1/1016—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials characterised by structural details, e.g. protective layers, backcoat layers or several imaging layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2201/00—Location, type or constituents of the non-imaging layers in lithographic printing formes
    • B41C2201/04—Intermediate layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2201/00—Location, type or constituents of the non-imaging layers in lithographic printing formes
    • B41C2201/14—Location, type or constituents of the non-imaging layers in lithographic printing formes characterised by macromolecular organic compounds, e.g. binder, adhesives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/02—Positive working, i.e. the exposed (imaged) areas are removed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/06—Developable by an alkaline solution
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/22—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by organic non-macromolecular additives, e.g. dyes, UV-absorbers, plasticisers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/24—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by a macromolecular compound or binder obtained by reactions involving carbon-to-carbon unsaturated bonds, e.g. acrylics, vinyl polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/26—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by a macromolecular compound or binder obtained by reactions not involving carbon-to-carbon unsaturated bonds
    • B41C2210/262—Phenolic condensation polymers, e.g. novolacs, resols

Definitions

  • the invention relates to a planographic printing plate precursor, and in particular to a positive planographic printing plate precursor allowing so-called direct plate making by scanning the precursor with an infrared laser beam based on digital signals from computer or the like.
  • a positive planographic printing plate for use with an infrared laser that uses an infrared laser having an emission in the infrared region as an exposure source is an image-forming material containing, as essential components, a binder resin soluble in an aqueous alkaline solution, and an IR dye or the like that absorbs light and generates heat.
  • Photosensitive compositions or image-forming materials known in the art such as those disclosed in WO 97/39894 , Japanese Patent Application Laid-Open (JP-A) Nos. 11-44956 and 11-218914, and others, function as a solubilization-inhibiting agent that substantially reduces the solubility of binder resin by interaction of an IR dye or the like in the photosensitive composition with the binder resin in the unexposed region (image region) when compositions are exposed to infrared laser.
  • the IR dye or the like absorbs light and generates heat, lowering the interaction between the IR dye or the like and the binder resin.
  • the exposed area (non-image region) is dissolved in an alkaline developer to form an image.
  • development scum insoluble scum derived from the binder resin
  • EP-A-1 518 671 which is prior art according to Article 54(3) EPC, discloses a positive-working lithographic printing starting plate for an infrared laser comprising a support having a hydrophilic surface and a heat-sensitive layer on the support, wherein the heat-sensitive layer comprises a water-insoluble/alkali-soluble resin, an infrared-absorbing dye and a sulphonium salt.
  • the sulphonium salt is an aryl sulphonium salt having at least one hydroxyl group at the ortho- and/or para-position of the aryl group.
  • EP-A-1 577 111 which is prior art according to Article 54(3) EPC, relates to a positive-type photosensitive composition
  • a positive-type photosensitive composition comprising a novolak resin; an alkali-soluble resin selected from resins prepared by addition polymerization of a vinyl compound and condensation polymers such as imide, amide, urethane, urea, ester and resol resins; an infrared-absorbing agent; and a sulphonium salt.
  • the sulphonium salt include triaryl sulphonium salts.
  • An objective of the invention which has been made to overcome the problems in the conventional methods, is to provide a high-sensitivity planographic printing plate precursor that allows direct plate making by a scanning exposure based on digital signals from a computer or the like, and suppresses generation of development scum.
  • the planographic printing plate precursor has a support and a recording layer formed on the support, containing a specific sulfonium salt (A), an alkali-soluble resin (B), and an infrared-light absorbing agent (C), wherein the cation of the specific sulfonium salt (A) has three phenyl groups, at least one of which is substituted by an -OH group, and the sulfonium salt (A) has a solubility of 25 mg/ml or more in an aqueous 0.1 mol/L NaOH solution having a liquid temperature equal to normal room temperature and at atmospheric pressure.
  • normal room temperature and atmospheric pressure means 25°C and 1 atm.
  • a sulfonium salt having a solubility such as described above (hereinafter, referred to as "specific sulfonium salt”) is very soluble in an aqueous alkaline solution.
  • specific sulfonium salt when the specific sulfonium salt is dissolved together with the binder in the developer of automatic developing machine, the specific sulfonium salt functions as a dispersant for the binder resin and, as a result, controls generation of development scum due to aggregation of the binder resin.
  • the specific sulfonium salt In the unexposed areas of the recording layer containing a specific sulfonium salt, an interaction occurs between the specific sulfonium salt and the alkali-soluble resin due to the structure of the onium salt, leading to an increase in the development-inhibiting effect.
  • the specific sulfonium salt which is inherently highly soluble in aqueous alkaline solution, is dissolved in the developer, and as a result, the recording layer is dissolved rapidly.
  • the present invention provides a high-sensitivity planographic printing plate precursor that allows direct plate making by means of scanning exposure based on digital signals from a computer or the like, and suppresses the generation of development scum.
  • a planographic printing plate precursor according to the invention has a support and a recording layer formed on the support having a specific sulfonium salt (A), an alkali-soluble resin (B), and an infrared-light absorbing agent (C).
  • the cation of the specific sulfonium salt (A) has three phenyl groups, at least one of which is substituted by an -OH group, and the sulfonium salt (A) has a solubility of at least 25 mg/ml in an aqueous 0.1 mol/L NaOH solution having a liquid temperature of 25°C and under atmospheric pressure.
  • the recording layer of the planographic printing plate precursor according to the present invention contains the specific sulfonium salt (A), an alkali-soluble resin (B), and an infrared-light absorbing agent (C) as essential components. These components will be described first in detail.
  • the specific sulfonium salt according to the present invention has a solubility of 25 mg/ml or more in an aqueous 0.1 mol/L NaOH solution having a liquid temperature of 25°C and under atmospheric pressure.
  • the solubility is preferably 35 mg/ml or more, and more preferably 50 mg/ml or more.
  • the cation of the specific sulfonium salt (A) preferably has three phenyl groups substituted by an alkali-soluble group.
  • the alkali-soluble group include -COOH, -OH, -SO 3 H, -PO 3 H 2 and the like, and among them, -COOH and -OH groups are preferable.
  • the phenyl groups may have one substituent, or two or more alkali-soluble groups.
  • the specific sulfonium salt according to the invention may have a structure containing two or more substituents per phenyl group having an alkali-soluble group as the substituent group.
  • the substitution position of the alkali-soluble group is not particularly limited.
  • the anionic region of the specific sulfonium salt is, for example, a strongly acidic residue, and is preferably a strongly acidic residue having multiple acidic groups, a strongly acidic residue derived from phosphonic acid, or the like for the purpose of increasing solubility in an aqueous alkaline solution.
  • the specific sulfonium salt according to the present invention has a structure containing a phenyl group having an alkali-soluble group as the substituent group, if the solubility thereof is 25 mg/ml or more in an aqueous 0.1 mol/L NaOH solution having a liquid temperature of 25°C at normal room temperature and atmospheric pressure, the phenyl group may have a substituent other than the alkali-soluble group.
  • substituent groups other than the alkali-soluble group include halogen atoms, a nitro group, alkyl groups having 12 or fewer carbon atoms, alkoxy groups having 12 or fewer carbon atoms, and aryloxy groups having 12 or fewer carbon atoms.
  • the strongly acidic residues favorable as the anionic region include halide ions (fluorine, chloride, bromide, and iodine ions), and the residues derived from sulfonic acid compounds, carboxylic acid compounds, inorganic acid compounds, and the like.
  • the compound preferably has a pKa of less than 5.
  • the strongly acidic residue is preferably a residue containing multiple acid groups.
  • examples of the inorganic acid compound residues include halide anions, HSO 4 - and anions of halogen-containing complex anions such as tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, and hexafluoroantimonate.
  • halide anions HSO 4 - and anions of halogen-containing complex anions such as tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, and hexafluoroantimonate.
  • a strongly acidic residue derived from an inorganic acid compound containing a fluorine atom is preferable.
  • the inorganic acid compounds containing a fluorine atom include tetrafluoroboric acid, tetrafluoroaluminic acid, tetrafluoroferric acid, tetrafluorogallic acid, hexafluorophosphoric acid, hexafluoroarsenic acid, hexafluoroantimonic acid, hexafluorosilicic acid, hexafluoronickelic acid, hexafluorotitanic acid, hexafluorozirconic acid, and the like; and among them, hexafluorophosphoric acid, tetrafluoroboric acid, hexafluoroantimonic acid, and the like are preferable.
  • sulfonic acid compounds from which the strongly acidic residue is derived include alkylsulfonic acids such as methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, hexanesulfonic acid, heptanesulfonic acid, octanesulfonic acid, nonanesulfonic acid, decanesulfonic acid, undecanesulfonic acid, dodecanesulfonic acid, tridecanesulfonic acid, tetradecanesulfonic acid, pentadecanesulfonic acid, hexadecanesulfonic acid, heptadecanesulfonic acid, octadecanesulfonic acid, nonadecanesulfonic acid, icosanesulfonic acid, henicosanesulfonic acid, docosanesulfonic acids
  • trifluoromethanesulfonic acid trifluoromethanesulfonic acid, p-toluenesulfonic acid, and methanesulfonic acid are particularly preferable from the aspects of availability and appropriateness for production.
  • carboxylic acid compounds from which the strongly acidic residue is derived include aliphatic unsaturated carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, iso-valeric acid, pivalic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, laurylic acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, nonadecanoic acid, icosanoic acid, henicosanoic acid, docosanoic acid, and tricosanoic acid; halogenated saturated fatty carboxylic acids such as fluoroacetic acid, chloroacetic acid, bromoacetic acid, iodoacetic acid, difluorine flu
  • benzoylformic acid acetic acid, and benzoic acid are particularly preferable.
  • the specific sulfonium salt is generally prepared by a Friedel-Crafts or Grignard reaction of a sulfide compound and an aromatic compound. Such synthetic methods are described, for example, in Journal of the American Chemical Society 112 (16), 1990, pp.6004-6015 ; The Journal of Organic Chemistry 1998, pp.5571-5573 ; International Publication (WO) No. 02/081439A1 ; and European Patent (EP) No. 1113005 .
  • the content of specific sulfonium salt in the recording layer according to the present invention is preferably 1 to 30 wt %, more preferably 3 to 25 wt %, and particularly preferably 5 to 20 wt %, with respect to the total solids in the recording layer, from the viewpoints of sensitivity and generation of development scum.
  • the specific sulfonium salts may be used alone or in combinations of two or more.
  • a general onium salt other than the specific sulfonium salts above may be added, in such a combination as a solubilization inhibitor, to the recording layer according to the invention.
  • the general onium salts will be described in the explanation of other components below.
  • the general onium salt is preferably used in an amount in the range of 0 to 30 wt %, and more preferably 0.5 to 15 wt.
  • alkali-soluble resin (B) to be used in the invention may include homopolymers containing acidic groups in the main chains and/or the side chains of the resin, their copolymers, or their mixtures.
  • polymers having the following acidic groups (1) to (6) in the main chains and/or side chains are preferable in terms of the development resistance, i.e. the suppression of the solubility to an aqueous alkaline solution:
  • Ar in the above-mentioned groups (1) to (6) represents a divalent aryl bonding group optionally comprising a substituent group and R represents a hydrocarbon group optionally comprising a substituent group.
  • an alkali-soluble resin comprising the acidic group selected from the above-mentioned (1) to (6) an alkali-soluble resin comprising (1) phenol, (2) sulfone amide, or (3) active imido group is preferable and an alkali-soluble resin comprising (1) phenol or (2) sulfone amide is more preferable in terms of assurance of the sufficient solubility in an alkaline developer, development latitude, and film strength.
  • alkali-soluble resin comprising the acidic group selected from the above-mentioned (1) to (6)
  • the following can be exemplified.
  • X 1 and X 2 each independently represent -O-, or -NR 7 -;
  • R 1 and R 4 each independently represent a hydrogen atom, or -CH 3 ;
  • R 2 , R 5 , R 9 , R 12 and R 16 each independently represent an alkylene, cycloalkylene, arylene or aralkylene group which may have a substituent and has 1 to 12 carbon atoms;
  • R 3 , R 7 and R 13 each independently represent a hydrogen atom, or an alkyl, cycloalkyl, aryl or aralkyl group which may have a substituent and has 1 to 12 carbon atoms;
  • R 6 and R 17 each independently represent an alkyl, cycloalkyl, aryl or aralkyl group which may have a substituent and has 1 to 12 carbon atoms;
  • R 8 , R 10 and R 14 each independently represent a hydrogen atom or -CH 3 ;
  • R 11 and R 15 each independently represent a
  • the following can preferably be used in the invention: m-aminosulfonylphenyl methacrylate, N-(p-aminosulfonylphenyl)methacrylamide and N-(p-aminosulfonylphenyl)acrylamide.
  • Examples of the monomer having an active imide group in the item (3) include compounds each having in the molecule thereof one or more active imide groups represented by the above-mentioned structural formula and one or more unsaturated groups which can be polymerized with the active imide group(s). Of these compounds, preferable are compounds each having in the molecule thereof one or more active imide groups represented by the following structural formula and one or more unsaturated groups which can be polymerized with the active imide group(s):
  • N-(p-toluenesulfonyl)methacrylamide, N-(p-toluenesulfonyl)acrylamide and others can be preferably used.
  • Examples of the monomer having a carboxylic acid group in the item (4) include compounds each having in the molecule thereof one or more carboxylic acid groups and one or more unsaturated groups which can be polymerized with the carboxylic acid group(s).
  • Examples of the monomer having a sulfonic acid group in the item (5) include compounds each having in the molecule thereof one or more sulfonic acid groups and one or more unsaturated groups which can be polymerized with the sulfonic acid group(s).
  • Examples of the monomer having a phosphoric acid group in the item (6) include compounds each having in the molecule thereof one or more phosphoric acid group and one or more unsaturated groups which can be polymerized with the phophoric acid group(s).
  • the minimum constituent unit comprising acidic group selected from (1) to (6) composing an alkali-soluble resin of the invention is not necessarily limited to one particular unit, but those obtained by copolymerizing two or more minimum constituent units comprising the same acidic group or two or more minimum constituent units comprising different acidic groups can also be used.
  • the above-mentioned copolymer contains the compound having the acidic group selected from (1) to (6) to be copolymerized in an amount preferably 10% by mole or more, more preferably 20% by mole or more. If it is less than 10% by mole, the development latitude tends to be improved insufficiently.
  • the compounds to be copolymerized may include other compounds without acidic group (1) to (6).
  • the compounds without acidic group (1) to (6) includee the following compounds (m1) to (m12), however they should not be limited to these examples.
  • the alkali-soluble resin is preferably a homopolymer or copolymer of a polymerizable monomer having the phenolic hydroxyl group above or an active imide group, and, in particular, a homopolymer or copolymer of a polimerizable monomer having the sulfonamide group such as m-aminosulfonylphenyl methacrylate, N-(p-aminosulfonylphenyl)methacrylamide, N-(p-aminosulfonylphenyl)acrylamide, or the like.
  • the alkali-soluble resin according to the present invention preferably has a weight-average molecular weight of 2,000 or more and a number-average molecular weight of 500 or more. More preferable is a resin having a weight-average molecular weight of 5,000 to 300,000, a number-average molecular weight of 800 to 250,000, and a molecular weight distribution (weight-average molecular weight / number-average molecular weight) of 1.1 to 10.
  • the alkali-soluble resin according to the invention is a phenol formaldehyde resin, a cresol aldehyde resin, or the like
  • the weight-average molecular weight thereof is preferably 500 to 20,000 and the number-average molecular weight, 200 to 10,000.
  • alkali-soluble resins may be used alone or in combinations of two or more.
  • the content of the alkali-soluble resin in the recording layer according to the present invention is preferably in the range of 30 to 98 wt %, more preferably 40 to 95 wt, and particularly preferably 50 to 90 wt %, with respect to the total solid in the recording layer, from the viewpoints of sensitivity, image-forming property, and film durability.
  • the infrared-light absorbing agent contained in the recording layer according to the present invention is a substance that absorbs light having a wavelength in the infrared range of 700 nm or more, preferably 750 to 1,200 nm, and capable of photothermal conversion of the light in this range.
  • various dyes or pigments that absorb light in the aforementioned wavelength region and generate heat may be used.
  • dyes such as azo dyes, metal complex salt azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, cyane dyes, squarylium pigments, pyrilium salts, metal thiolate complexes, oxomol dyes, diimonium dyes, aminium dyes, and croconium dyes.
  • dyes such as azo dyes, metal complex salt azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, cyane dyes, squarylium pigments, pyrilium salts, metal thiolate complexes, oxomol dyes, diimonium dyes,
  • the dye include cyanine dyes described in JP-A Nos. 58-125246 , 59-84356 , 59-202829 , and 60-78787 ; methine dyes described in JP-ANos. 58-173696 , 58-181690 , and 58-194595 ; naphthoquinone dyes described in JP-ANos. 58-112793 , 58-224793 , 59-48187 , 59-73996 , 60-52940 , and 60-63744 ; squalirium dyes described in JP-A No. 58-112792 ; and cyanine dyes described in GB Patent No. 434,875 .
  • the dye include near infrared absorbing sensitizers described in U.S. Patent No. 5,156,938 ; substituted arylbenzo(thio)pyrylium salts described in U.S. Patent No. 3,881,924 ; trimethinethiapyrylium salts described in JP-ANo. 57-142645 ( U.S. Patent No. 4,327,169 ); pyrylium type compounds described in JP-ANos. 58-181051 , 58-220143 , 59-41363 , 59-84248 , 59-84249 , 59-146063 , and 59-146061 ; cyanine dyes described in JP-A No.
  • the dye include near infrared absorbing dyes represented by formulae (I) and (II) as described in U.S. Patent No. 4,756,993 .
  • dyes particularly preferable are cyanine dyes, phthalocyanine dyes, oxonol dyes, squalirium dyes, pyrylium salts, thiopyrylium dyes, and nickel thiolate complexes.
  • Dyes represented by the following general formulae (a) to (e) are also preferable since such dyes are excellent in terms of photothermal conversion efficiency.
  • the cyanine dyes represented by the following general formula (a) are most preferable for the following reason: when the dyes are used in the photosensitive composition of the invention, the dyes manifest a high degree of polymerizing activity, and the dyes are also excellent in terms of stability and economy.
  • X 1 represents a hydrogen atom, a halogen atom, -NPh 2 , X 2 -L 1 (wherein X 2 represents an oxygen atom or a sulfur atom, L 1 represents a hydrocarbon group having 1 to 12 carbon atoms, an aromatic cyclic group having a heteroatom, or a hydrocarbon group containing a heteroatom and having 1 to 12 carbon atoms, and the heteroatom referred to herein is N, S, O, a halogen atom, or Se), or a group represented by the following: wherein Xa - has the same definition as Za - , which will be described at a later time, and R a represents a substituent selected from a hydrogen atom, an alkyl group, an aryl group, a substituted or unsubstituted amino group, or a halogen atom;
  • R 1 and R 2 each independently represents a hydrocarbon group having 1 to 12 carbon atoms, and from the viewpoint of the storage stability of the photosensitive composition of the invention when it is used in a coating solution for forming a recording layer of a planographic printing plate precursor, it is preferable that R 1 and R 2 each independently represents a hydrocarbon group having 2 or more carbon atoms, and more preferably R 1 and R 2 are bonded to each other to form a 5-membered or 6-membered ring.
  • Ar 1 and Ar 2 which may be the same or different, each represent an aromatic hydrocarbon group which may have a substituent.
  • the aromatic hydrocarbon group include benzene and naphthalene rings.
  • the substituent include hydrocarbon groups having 12 or less carbon atoms, halogen atoms, and alkoxy groups having 12 or less carbon atoms.
  • Y 1 and Y 2 which may be the same or different, each represents a sulfur atom, or a dialkylmethylene group having 12 or less carbon atoms.
  • R 3 and R 4 which may be the same or different, each represents a hydrocarbon group which has 20 or less carbon atoms and may have a substituent.
  • substituent include alkoxy groups having 12 or less carbon atoms, a carboxyl group, and a sulfo group.
  • R 5 , R 6 , R 7 and R 8 which may be the same or different, each represents a hydrogen atom, or a hydrocarbon group having 12 or less carbon atoms, and since the raw materials thereof can easily be obtained, each preferably represents a hydrogen atom.
  • Za - represents a counter anion.
  • the cyanine dye represented by general formula (a) has an anionic substituent in the structure thereof and there is accordingly no need to neutralize electric charges in the dye, Za - is not required.
  • Za - is preferably an ion of a halogen, perchlorate, tetrafluroborate, hexafluorophosphate, carboxylate or sulfonate.
  • Za - is preferably a halogen ion, or an organic acid ion such as a carboxylic acid ion or sulfonic acid ion, more preferably a sulfonic acid ion, and even more preferably an arylsulfonic acid ion.
  • cyanine dye represented by general formula (a) examples include dyes in JP-A No. 2001-133969 (paragraphs [0017] to [0019]), JP-ANo. 2002-40638 (paragraphs [0012] to [0038]), and JP-ANo. 2002-23360 (paragraphs [0012] to [0023]), as well as dyes illustrated below.
  • L represents a methine chain having 7 or more conjugated carbon atoms, and the methine chain may have one or more substituent.
  • the substituents may be bonded to each other to form a cyclic structure.
  • Zb + represents a counter cation.
  • the counter cation include ammonium, iodonium, sulfonium, phosphonium and pyridinium ions, and alkali metal cations (such as Ni + , K + and Li + ).
  • R 9 to R 14 and R 15 to R 20 each independently represents a substituent selected from hydrogen atom, halogen atom, and cyano, alkyl, aryl, alkenyl, alkynyl, carbonyl, thio, sulfonyl, sulfinyl, oxy and amino groups; or a substituent obtained by combining two or three from among these substituents. Two or three out of R 9 to R 14 and R 15 to R 20 may be bonded to each other to form a cyclic structure.
  • Y 3 and Y 4 each independently represent an oxygen, sulfur, selenium or tellurium atom;
  • M represents a methine chain having 5 or more conjugated carbon atoms;
  • R 21 to R 24 and R 25 to R 28 which may be the same or different, each represents a hydrogen or halogen atom, or a cyano, alkyl, aryl, alkenyl, alkynyl, carbonyl, thio, sulfonyl, sulfinyl, oxy or amino group; and
  • Za - represents a counter anion, and has the same meaning as Za - in general formula (a).
  • R 29 to R 32 each independently represents a hydrogen atom, an alkyl group or an aryl group;
  • R 33 and R 34 each independently represents an alkyl group, a substituted oxy group, or a halogen atom;
  • n and m each independently represents an integer of 0 to 4; and
  • R 29 and R 30 , or R 31 and R 32 may be bonded to each other to form a ring, or R 29 and/or R 30 may be bonded to R 33 to form a ring and R 31 and/or R 32 may be bonded to R 34 to form a ring.
  • R 33 's and R 34 's are present, R 33 's may be bonded to each other to form a ring, or R 34 's may be bonded to each other to form a ring.
  • X 2 and X 3 each independently represents a hydrogen atom, an alkyl group or an aryl group, and at least one of X 2 and X 3 represents a hydrogen atom or an alkyl group.
  • Q represents a trimethine group or a pentamethine group which may have a substituent, and may be combined with an bivalent organic group to form a cyclic structure.
  • Zc - represents a counter anion and has the same meanings as Za - in general formula (a).
  • R 35 to R 50 each independently represents a hydrogen or halogen atom, or a cyano, alkyl, aryl, alkenyl, alkynyl, hydroxyl, carbonyl, thio, sulfonyl, sulfinyl, oxy or amino group, or an onium salt structure, each of which may have a substituent;
  • M represents two hydrogen atoms, a metal atom, a halo metal group, or an oxy metal group.
  • the metal contained therein include atoms in IA, IIA, IIIB and IVB groups in the periodic table, transition metals in the first, second and third periods therein, and lanthanoid elements.
  • preferable are copper, magnesium, iron, zinc, cobalt, aluminum, titanium, and vanadium.
  • the pigment used as the infrared absorbent in the invention may be a commercially available pigment or a pigment described in publications such as Color Index (C.I.) Handbook, " Latest Pigment Handbook” (edited by Japan Pigment Technique Association, and published in 1977 ), “ Latest Pigment Applied Technique” (by CMC Publishing Co., Ltd. in 1986 ), and “ Printing Ink Technique” (by CMC Publishing Co., Ltd. in 1984 ).
  • C.I. Color Index
  • the pigment 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.
  • insoluble azo pigments azo lake pigments, condensed azo pigments, chelate azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene and perynone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments, quinophthalone pigments, dyeing lake pigments, azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, inorganic pigments, and carbon black.
  • carbon black is preferable.
  • These pigments may be used with or without surface treatment.
  • surface treatment include a method of coating the surface of the pigments with resin or wax; a method of adhering a surfactant onto the surface; and a method of bonding a reactive material (such as a silane coupling agent, an epoxy compound, or a polyisocyanate) to the pigment surface.
  • a reactive material such as a silane coupling agent, an epoxy compound, or a polyisocyanate
  • a particle diameter of pigments is preferably in a range of 0.01 ⁇ m to 10 ⁇ m, further preferably in a range of 0.05 ⁇ m to 1 ⁇ m, particularly preferably in a range of 0.1 ⁇ m to 1 ⁇ m.
  • the method for dispersing the pigment may be a known dispersing technique used to produce ink or toner.
  • a dispersing machine which can be used, include an ultrasonic disperser, a sand mill, an attriter, a pearl mill, a super mill, a ball mill, an impeller, a disperser, a KD mill, a colloid mill, a dynatron, a three-roll mill, and a pressing kneader. Details are described in " Latest Pigment Applied Technique” (by CMC Publishing Co., Ltd. in 1986 ).
  • the pigment or dye can be added to the recording layer in a ratio of 0.01 to 30%, preferably 0.1 to 10%, and more preferably 0.1 to 5% in the case of the dye or 0.2 to 10% in the case of pigment by mass, relative to the total solid contents of the recording layer.
  • the recording layer according to the present invention may contain various additives as needed.
  • solubilization inhibitor that functions to inhibit solubilization of the alkali-soluble resin (B) when added to the developer, such as an onium salt other than the specific sulfonium salts, an aromatic sulfone compound, an aromatic sulfonic ester compound, a multifunctional amine compound, or the like, for adjustment of the solubility of the recording layer.
  • thermally decomposable substances that inhibit solubilization of the alkali-soluble resin substantially while they are not decomposed such as onium salts, o-quinonediazide compounds, sulfonic acid alkyl esters and the like are preferably used in combination for further suppressing the solubilization-inhibiting properties of the image region in the developer.
  • onium salt used in the invention include diazonium salts described in S. I. Schlesinger, Photogr. Sci. Eng., 18, 387 (1974 ), T. S. Bal et al., Polymer, 21, 423 (1980 ), and JP-ANo. 5-158230 ; ammonium salts described in U.S. Patent Nos. 4,069,055 and 4,069,056 , and JP-A No. 3-140140 ; phosphonium salts described in D. C. Necker et al., Macromolecules, 17, 2468 (1984 ), C. S. Wen et al., Teh, Proc. Conf. Rad.
  • diazonium salts and quaternary ammonium salts are particularly preferable from the viewpoints of both their capacity of hindering dissolution, and their thermal decomposability.
  • the diazonium salts represented by general formula (I) in the JP-A No. 5-158230 and the diazonium salts represented by general formula (1) in JP-A No. 11-143064 are more preferable, and diazonium salts represented by general formula (1) in the JP-ANo. 11-143064 , which have low absorption wavelength peaks within the visible ray range, are most preferable.
  • the quaternary ammonium salts those represented by formulae (1) to (10) of [Ka 5] and [Ka 6] of JP-ANo. 2002-229186 are preferable.
  • Examples of the counter ion of the onium salt include tetrafluoroboric acid, hexafluorophosphoric acid, triisopropylnaphthalenesulfonic acid, 5-nitro-o-toluenesulfonic acid, 5-sulfosalicylic acid, 2,5-dimethylbenzenesulfonic acid, 2,4,6-trimethylbenzenesulfonic acid, 2-nitrobenzenesulfonic acid, 3-chlorobenzenesulfonic acid, 3-bromobenzenesulfonic acid, 2-fluorocaprylnaphthalenesulfonic acid, dodecylbenzenesulfonic acid, 1-naphthol-5-sulfonic acid, 2-methoxy-4-hydroxy-5-benzoyl-benzenesulfonic acid, and p-toluenesulfonic acid.
  • hexafluorophosphoric acid, and alkylaromatic sulfonic acids such as triisopropylnaphthalenesulfonic acid and 2,5-dimethylbezenesulfonic acid are particularly preferable.
  • the quinonediazide is preferably an o-quinonediazide compound.
  • the o-quinonediazide compound used in the invention is a compound having at least one o-quinonediazide group and having an alkali-solubility increased by being thermally decomposed.
  • the compound may be any one of compounds having various structures.
  • the o-quinonediazide compound assists the solubility of the photosensitive material both from the viewpoint of the effects of being thermally decomposed, and thereby losing the function of suppressing the dissolution of the binder, and the effect that the o-quinonediazide itself is changed into an alkali-soluble material.
  • o-quinonediazide compound used in the invention include compounds described in J. Coser, "Light-Sensitive Systems” (John Wiley & Sons. Inc.), pp. 339-352 .
  • Particularly preferable are sulfonic acid esters or sulfonamides of o-quinonediazide made to react with various aromatic polyhydroxy compounds or with aromatic amino compounds.
  • esters made from benzoquinone-(1,2)-diazidesulfonic acid chloride or naphthoquinone-(1,2)-diazide-5-sulfonic acid chloride and pyrogallol-acetone resin, as described in JP-B No. 43-28403 ; and an ester made from benzoquinone-(1,2)-diazidesulfonic acid chloride or naphthoquinone-(1,2)-diazide-5-sulfonic acid chloride and phenol-formaldehyde resin.
  • Additional preferable examples include an ester made from naphthoquinone-(1,2)-diazide-4-sulfonic acid chloride and phenol-formaldehyde resin or cresol-formaldehyde resin; and an ester made from naphthoquinone-(1,2)-diazide-4-sulfonic acid chloride and pyrogallol-acetone resin.
  • the amount of onium salt and/or o-quinonediazide compound added as the decomposable dissolution suppresser(s) is preferably from 1 to 10%, more preferably from 1 to 5%, and even more preferably from 1 to 2% by relative to the total solid contents of the recording layer.
  • the onium salts and the o-quinonediazide compounds may be used either independently or in the form of mixtures of two or more thereof.
  • the amount of additives other than the o-quinonediazide compound added is preferably from 0.1 to 5%, more preferably from 0.1 to 2%, and even more preferably from 0.1 to 1.5% by mass.
  • the additives and the binder used in the invention are preferably incorporated into the same layer.
  • a dissolution suppresser having no decomposability may be used in combination.
  • Preferable examples thereof include sulfonic acid esters, phosphoric acid esters, aromatic carboxylic acid esters, aromatic disulfones, carboxylic acid anhydrides, aromatic ketones, aromatic aldehydes, aromatic amines, and aromatic ethers, details of which are described in JP-A No. 10-268512 ; acidic color-developable dyes which have a lactone skeleton, an N,N-diarylamide skeleton or a diarylmethylimino skeleton and also function as a coloring agent, details of which are described in JP-A No. 11-190903 ; and nonionic surfactants described, details of which are described in JP-A No. 2000-105454 .
  • the photosensitive composition may also contain a cyclic acid anhydride, a phenolic compound, or an organic acid.
  • cyclic acid anhydride examples include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,6-endooxy- ⁇ 4-tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride, ⁇ -phenylmaleic anhydride, succinic anhydride, and pyromellitic anhydride which are described in U.S. Patent No. 4,115,128 .
  • phenolic compound examples include bisphenol A, p-nitrophenol, p-ethoxyphenol, 2,4,4'-trihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 4-hydroxybenzophenone, 4,4',4"-trihydroxytriphenylmethane, 4,4',3",4"-tetrahydroxy-3,5,3',5'-tetramethyltriphenylmethane.
  • organic acid examples include sulfonic acids, sulfonic acids, alkylsulfuric acids, phosphonic acids, phosphates, and carboxylic acids, which are described in JP-A No. 60-88942 or 2-96755 .
  • Specific examples thereof include p-toluenesulfonic acid, dodecylbenzenesulfonic acid, p-toluenesulfinic acid, ethylsulfuric 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-1,2-dicarboxylic acid, erucic acid, lauric acid, n-undecanoic acid, and ascorbic acid.
  • the ratio thereof in the recording layer is preferably from 0.05 to 20%, more preferably from 0.1 to 15%, and even more preferably from 0.1 to 10% by mass.
  • nonionic surfactants as described in JP-A Nos. 62-251740 and 3-208514
  • amphoteric surfactants as described in JP-A Nos. 59-121044 and 4-13149
  • siloxane compounds as described in EP No. 950517
  • copolymers made from a fluorine-containing monomer as described in JP-A No. 11-288093 .
  • nonionic surfactants include sorbitan tristearate, sorbitan monopalmitate, sorbitan trioleate, monoglyceride stearate, and polyoxyethylene nonyl phenyl ether.
  • amphoteric surfactants include alkyldi(aminoethyl)glycine, alkylpolyaminoethylglycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine and N-tetradecyl-N,N'-betaine type surfactants (trade name: "Amolgen K", manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.).
  • the siloxane compounds are preferably block copolymers made from dimethylsiloxane and polyalkylene oxide. Specific examples thereof include polyalkylene oxide modified silicones (trade names: DBE-224, DBE-621, DBE-712, DBE-732, and DBE-534, manufactured by Chisso Corporation; trade name: Tego Glide 100, manufactured by Tego Co., Ltd.).
  • the content of the nonionic surfactant and/or the amphoteric surfactant in the photosensitive composition is preferably from 0.05 to 15% by mass, and more preferably from 0.1 to 5% by mass.
  • a printing-out agent for obtaining a visible image immediately after the photosensitive composition of the invention has been heated by exposure to light or a dye or pigment as an image coloring agent.
  • a typical example of a printing-out agent is a combination of a compound which is heated by exposure to light, thereby emitting an acid (an optically acid-generating agent), and an organic dye which can form salts (salt formable organic dye).
  • JP-A Nos. 50-36209 and 53-8128 examples thereof include combinations of an o-naphthoquinonediazide-4-sulfonic acid halogenide with a salt-formable organic dye, described in JP-A Nos. 50-36209 and 53-8128 ; and combinations of a trihalomethyl compound with a salt-formable organic dye, described in each of JP-A Nos. 53-36223 , 54-74728 , 60-3626 , 61-143748 , 61-151644 and 63-58440 .
  • the trihalomethyl compound is classified into an oxazol compound or a triazine compound. Both of the compounds provide excellent in stability over the passage of time and produce a vivid printed-out image.
  • a dye different from the above-mentioned salt-formable organic dye may be used.
  • a dye, and of the salt-formable organic dye include oil-soluble dyes and basic dyes.
  • Oil yellow #101, Oil Yellow #103, Oil Pink #312, Oil Green BG, Oil Blue BOS, Oil Blue #603, Oil Black BY, Oil Black BS, and Oil Black T-505 each of which is manufactured by Orient Chemical Industries Ltd.
  • Dyes described in JP-A No. 62-293247 are particularly preferable. These dyes may be added to the photosensitive composition at a ratio of 0.01 to 10% by mass, and preferably 0.1 to 3% by mass, relative to the total solid contents therein.
  • a plasticizer may be added to the photosensitive composition of the invention to give flexibility to a coating film made from the composition.
  • the plasticizer include oligomers and polymers of butyl phthalyl, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl olete, and acrylic acid and methacrylic acid.
  • the recording layer of a planographic printing plate precursor according to the present invention may be either a single-layered, phase-separated composite, or multi-layered composite layer.
  • Examples of applicable single-layered recording layers include the configurations of the photosensitive layer described in JP-A No. 7-285275 , and WO 97/39894 .
  • Examples of applicable phase-separated composite recording layers include the configuration of the photosensitive layers described in JP-A No. 11-44956 .
  • examples of the multi-layered composite recording layers include the configurations of the photosensitive layer described in JP-ANo. 11-218914 , US PatentNos. 6352812B1 , 6352811B1 , 6358669B1 , and 6534238B1 , and EP Patent No. 864420B1 .
  • the configuration of the recording layer according to the present invention is not limited thereto.
  • the multi-layered composite recording layer when used as a recording layer, preferably contains the specific sulfonium salt according to the present invention in the uppermost layer for more effective manifestation of advantageous effects.
  • the recording layer according to the present invention can be formed by preparing a recording layer-coating solution by dissolving the components for the recording layer in a solvent, and applying and drying the coating solution on a suitable support.
  • An undercoat layer and other coat layers described below may also be formed as needed in a similar manner.
  • solvents to be used include, but are not limited to, ethylene dichloride, cyclohexanone, methylethylketone, methanol, ethanol, propanol, ethylene glycol monomethylether, 1-methoxy-2-propanol, 2-methoxyethyl acetate, 1-methoxy-2-propyl acetate, dimethoxyethane, methyl lactate, ethyl lactate, N,N-dimethylacetamide, N,N-dimethylformamide, tetramethylurea, N- methylpyrrolidone, dimethylsulfoxide, sulfolane, ⁇ -butylolactone, toluene and the like. These solvents are used alone or as a mixture.
  • the concentration of the components (total solid portion including additives) in solvent is preferably 1 to 50 wt %.
  • the amount coated (as solid matter) on the support after coating and drying may vary according to the application, but is generally preferably 0.5 to 5.0 g/m 2 , and more preferably 0.6 to 2.0 g/m 2 , as the coating amount after drying.
  • the coating amount of the lower layer is preferably 0.1 to 5.0 g/m 2 and more preferably 0.2 to 3.0 g/m 2
  • that of the upper layer (top layer) is preferably 0.01 to 5.0 g/m 2 , and more preferably 0.05 to 2.0 g/m 2 .
  • Various methods may be used for applying the recording layer coating solution. Examples thereof include bar coater coating, spin coating, spray coating, curtain coating, dip coating, air knife coating, blade coating, roll coating, and the like. As the coating amount decreases, the apparent sensitivity increases, but the film properties of the photosensitive layer deteriorates.
  • a surfactant for example, the fluorochemical surfactant described in JP-A No. 62-170950 may be added to the coating solution for the recording layer according to the present invention, for improvement of coating efficiency.
  • the preferable addition amount is 0.01 to 1 wt %, and more preferably 0.05 to 0.5 wt %, with respect to the total solids in the recording layer-coating solution.
  • the support used in the planographic printing plate precursor is a plate having dimensional stability.
  • a plate satisfying required physical properties such as strength and flexibility can be used without any restriction.
  • Examples thereof include paper, plastic (such as polyethylene, polypropylene or polystyrene)-laminated papers, metal plates (such as aluminum, zinc and copper plates), plastic films (such as cellulose biacetate, cellulose triacetate, cellulose propionate, cellulose lactate, cellulose acetate lactate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, and polyvinyl acetate films), and papers or plastic films on which, as described above, a metal is laminated or vapor-deposited.
  • plastic such as polyethylene, polypropylene or polystyrene
  • metal plates such as aluminum, zinc and copper plates
  • plastic films such as cellulose biacetate, cellulose triacetate, cellulose propionate, cellulose lactate, cellulose acetate lactate
  • the support is preferably a polyester film or an aluminum plate, and more preferably an aluminum plate, since an aluminum plate is superior in terms of dimensional stability and is also relatively inexpensive.
  • the aluminum plate include a pure aluminum plate and alloy plates made of aluminum as a main component with a very small amount of other elements.
  • a plastic film on which aluminum is laminated or vapor-deposited may also be used.
  • Examples of other elements contained in the aluminum alloys include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, and titanium.
  • the content by percentage of different elements in the alloy is at most 10% by mass.
  • a particularly preferable aluminum plate in the invention is a pure aluminum plate; however, since from the viewpoint of refining a completely pure aluminum cannot be easily produced, a very small amount of other elements may also be contained in the plate.
  • the aluminum plate used as the support is not specified in terms of the composition thereof. Thus, aluminum plates which are conventionally known can be appropriately used.
  • the thickness of the aluminum plate used in the invention is from about 0.1 to 0.6 mm, preferably from 0.15 to 0.4 mm, and more preferably from 0.2 to 0.3 mm.
  • the aluminum plate may optionally be subjected to degreasing treatment, in order to remove rolling oil or the like on the surface, with a surfactant, an organic solvent, an aqueous alkaline solution or the like.
  • the surface-roughening treatment of the aluminum surface can be performed by various methods such as a mechanical surface-roughening method, a method of dissolving and roughening the surface electrochemically, and a method of dissolving the surface selectively in a chemical manner.
  • Mechanical surface-roughening methods which can be used may be known methods, such as a ball polishing method, a brush polishing method, a blast polishing method or a buff polishing method.
  • An electrochemical surface-roughening method may be a method of performing surface-roughening in an electrolyte of hydrochloric acid or nitric acid, by use of an alternating current or a direct current. As disclosed in JP-A No. 54-63902 , a combination of the two kinds of methods may be used.
  • An aluminum plate whose surface is roughened as described above is if necessary subjected to alkali-etching treatment and neutralizing treatment. Thereafter, an anodizing treatment is optionally applied in order to improve the water holding capacity and wear resistance of the surface.
  • the electrolyte used in the anodizing treatment of the aluminum plate is any one selected from various electrolytes which can form a porous oxide film. Among which in general use are electrolytes of sulfuric acid, phosphoric acid, oxalic acid, chromic acid, or a mixed acid thereof. The concentration of the electrolyte may be appropriately decided depending on the kind of electrolyte selected.
  • Treatment conditions for anodization cannot be specified as a general rule since conditions vary depending on the electrolyte used; however, the following range of conditions are generally suitable: an electrolyte concentration of 1 to 80% by mass, a solution temperature of 5 to 70°C, a current density of 5 to 60 A/dm 2 , a voltage of 1 to 100 V, and an electrolyzing time of 10 seconds to 5 minutes. If the amount of anodic oxide film is less than 1.0 g/m 2 , printing resistance is inadequate or non-image portions of the planographic printing plate tend to become easily damaged and the so-called "blemish stains", resulting from ink adhering to damaged portions at the time of printing, are easily generated.
  • hydrophilicity treatment may be an alkali metal silicate (for example, an aqueous sodium silicate solution) method, as disclosed in U.S. Patent Nos. 2,714,066 , 3,181,461 , 3,280,734 , and 3,902,734 .
  • the support is subjected to an immersing treatment or an electrolyzing treatment with an aqueous sodium silicate solution.
  • the following methods may also be used: a method of treating the support with potassium fluorozirconate, as disclosed in JP-B No. 36-22063 , or with polyvinyl phosphonic acid, as disclosed in U.S. Patent Nos. 3,276,868 , 4,153,461 , and 4,689,272 .
  • planographic printing plate precursor according to the present invention is a plate having a recording layer as described above provided on a support, and an undercoat layer may be formed as needed between the support and the recording layer.
  • the undercoat layer between the support and the recording layer functions as a heat-insulating layer, inhibiting diffusion of the heat generated by exposure to an infrared laser to the support and allowing more efficient use of an infrared laser, and thus, is advantageous in improving sensitivity.
  • the recording layer according to the invention is positioned on the exposure face or in the vicinity thereof, and thus significantly retains its sensitivity to an infrared laser.
  • the recording layer which is resistant to penetration of the alkaline developer, functions as a protective layer for the undercoat layer, improving development stability, forming an image having superior discrimination, and ensuring image stability over time.
  • the undercoat layer is a layer containing an alkali-soluble polymer as its principal component and is extremely soluble in the developer. If the undercoat layer is formed close to the support, the exposed area, where the components in the photosensitive layer that becomes more soluble by exposure, is dissolved or dispersed in the developer more readily without generation of undissolved film, for example, when a less active developer is used, which seems to be effective for improving developing efficiency. For that reason, the undercoat layer is thought to be useful.
  • organic compounds may be used as the components for the undercoat layer, and examples thereof include amino group-containing phosphonic acids that may be substituted such as carboxymethylcellulose, dextrin, gum arabic, and 2-aminoethylphosphonic acid; organic phosphonic acid that may be substituted such as phenylphosphonic acid, naphthylphosphonic acid, alkylphosphonic acids, glycerophosphonic acid, methylenediphosphonic acid and ethylenediphosphonic acid; organic phosphoric acids that may be substituted such as phenylphosphoric acid, naphthylphosphoric acid, alkylphosphoric acid and glycerophosphoric acid; organic phosphinic acids such as phenylphosphinic acid, naphthylphosphinic acid, alkylphosphinic acid and glycerophosphinic acid; amino acids such as glycine and ⁇ -alanine; hydroxy group-containing amine hydrochloride salts such as triethanolamine hydrochloride
  • an undercoat layer containing at least one compound selected from the group consisting of organic polymer compounds having the structural unit represented by the following Formula is also preferable.
  • R 11 represents a hydrogen or halogen atom or an alkyl group
  • R 12 and R 13 each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, -OR 14 , -COOR 15 , -CONHR 16 , -COR 17 or -CN, or R 12 and R 13 may bind to each other forming a ring
  • R 14 to R 17 each independently represent an alkyl or aryl group
  • X represents a hydrogen or metal atom, or NR 18 R 19 R 20 R 21
  • R 18 to R 21 each independently represent a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group, or R 18 and R 19 may bind to each other forming a ring
  • m represents an integer of 1 to 3.
  • An example of a suitable undercoat layer component for the planographic printing plate precursor according to the invention is a polymer compound having an acid group-containing a structural component and an onium group-containing component described in JP-ANo. 2000-241962. Specifically, it is a copolymer of an acid group-containing monomer and an onium group-containing monomer.
  • the acid group is preferably an acid group having an acid dissociation constant (pKa) of 7 or more, more preferably -COOH, -SO 3 H, -OSO 3 H, -PO 3 H 2 , -OPO 3 H 2 , -CONHSO 2 -, or -SO 2 NHSO 2 -, and particularly preferably -COOH.
  • the acid group-containing monomers include acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, itaconic acid, maleic acid, maleic anhydride, styrene derivatives having the acid group above, and the like.
  • the onium salt is preferably an onium group having an atom in groups V and VI of the Periodic Table, more preferably an onium salt of a nitrogen, phosphorus or sulfur atom, and particularly preferably an onium salt of a nitrogen atom.
  • Specific examples of the onium salt-containing monomers include methacrylates and methacrylamides having an ammonium group on the side chain, and styrenes having an onium group-containing substituent such as those having a quaternary ammonium group.
  • Such an undercoat layer can be formed, for example, according to the following methods: a method of dissolving the organic compounds in an organic solvent or a mixed solvent of water, methanol, ethanol, methylethylketone, or the like, and applying and drying the solution on an aluminum plate (support); and a method of dissolving the organic compounds in an organic solvent or a mixed solvent of water, methanol, ethanol, methylethylketone, or the like, allowing an aluminum plate (support) to absorb the solution by immersion in the solution, and washing the plate with water or the like and drying it.
  • the concentration of the solution is 0.01 to 20 wt %, preferably 0.05 to 5 wt %; the immersion temperature is 20 to 90°C, preferably 25 to 50°C; and the immersion period is 0.1 second to 20 minutes, preferably 2 seconds to 1 minutes.
  • the solution used may be adjusted to a pH in the range of 1 to 12 by addition of a basic substance such as ammonia, triethylamine, or potassium hydroxide, or an acidic substance such as hydrochloric acid or phosphoric acid.
  • a yellow dye may also be added, for improvement of tone reproducibility in the image-recording material.
  • the amount of the undercoat layer coated is suitably 2 to 200 mg/m 2 , and preferably 5 to 100 mg/m 2 , from the viewpoint of printing durability.
  • An image is formed thermally on the planographic printing plate precursor according to the present invention.
  • direct image recording with a thermal recording head or the like scanning exposure with an infrared laser, high-illumination flash exposure with xenon discharge lamp or the like, infrared lamp exposure, or the like is used for this image formation, but exposure to a high-output infrared solid laser emitting a light at a wavelength of 700 to 1,200 nm, such as from an infrared light-emitting semiconductor laser or YAG laser is suitable.
  • the laser output is preferably 100 mW or more, and it is preferable to use a multi-beam laser device to shorten the exposure period.
  • the exposure period per pixel is preferably 20 ⁇ sec or less, and the irradiation energy applied onto the recording material is preferably 10 to 500 mJ/cm 2 .
  • the developer which may be applied to the developing treatment of the planographic printing plate precursor of the invention is a developer having a pH range from 9.0 to 14.0 and preferably a pH range from 12.0 to 13.5.
  • a developer hereinafter this term will represent a developer including a replenisher
  • a conventionally known aqueous alkali solution may be used.
  • alkali agent examples include inorganic alkali salts such as sodium silicate, potassium silicate, trisodium phosphate, tripotassium phosphate, triammonium phosphate, disodium hydrogenphosphate, dipotassium hydrogenphosphate, diammonium hydrogenphosphate, sodium carbonate, potassium carbonate, ammonium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, ammonium hydrogen carbonate, sodium borate, potassium borate, ammonium borate, sodium hydroxide, ammonium hydroxide, potassium hydroxide and lithium hydroxide; and organic alkali agents such as monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, ethyleneimine, ethylenediamine, and
  • alkali agents may be used alone or in combinations of two or more thereof.
  • one developer which exerts the effect of the invention is an aqueous solution of a pH 12 or higher so-called “silicate developer” containing alkali silicate as a base, or containing alkali silicate obtained by mixing a base with a silicon compound, and the other more preferable developer is a so-called “non-silicate developer” which does not contain alkali silicate, and contains a non-reducing sugar (organic compound having buffering action) and a base.
  • an aqueous solution of alkali metal silicate can be regulated by a ratio (generally expressed by mole ratio of [SiO 2 ]/[M 2 O]) of silicon oxide SiO 2 and alkali metal oxide M 2 O.
  • a ratio generally expressed by mole ratio of [SiO 2 ]/[M 2 O]
  • silicon oxide SiO 2 and alkali metal oxide M 2 O for example, an aqueous solution of sodium silicate in which a mole ratio of SiO 2 /Na 2 O is 1.0 to 1.5 (that is,[SiO 2 ]/[Na 2 O] is 1.0 to 1.5), and a content of SiO 2 is 1 to 4% by mass as disclosed in JP-A No.
  • non-silicate developer containing no alkali silicate and containing non-reducing sugar and a base is also preferable for application to developing of a planographic printing plate precursor of the invention.
  • planographic printing plate precursors When a planographic printing plate precursor is developing-treated using this developer, a surface of a recording layer is not deteriorated, and inking property of a recording layer can be maintained in the good state.
  • planographic printing plate precursors generally have a narrower development latitude and a greater fluctuation in the width of image lines caused by fluctuation in the pH of the developer, and thus, use of a non-silicate developer, which contains a nonreducing sugar that has a buffering action on the fluctuation of pH, is more advantageous than the use of a developer containing a silicate.
  • the nonreducing sugar is less likely to contaminate the conductivity sensor, pH sensor, or the likeused for controlling the solution activity than silicates, and the use of the non-silicate developer is advantageous from that point too. It is also effective in significantly improving discrimination. Presumably, this is because the difference between the exposed and unexposed areas is enhanced by a mild contact (penetration) of the developer, which is important in the present invention.
  • the aforementioned non-reducing sugar is a sugar having no free aldehyde group or ketone group, and not exhibiting reducing property, and is classified into a trehalose-type oligosaccharide in which reducing groups are bound, a glycoside in which a reducing group of a sugar and a non-sugar are bound, and sugar alcohol obtained by hydrogenating sugars to reduce them. Any of these can be suitable used.
  • the non-reducing sugar disclosed in JP-A 8-305039 Laid-Open for example, can be suitably used.
  • Examples of the trehalose type oligosaccharides include saccharose and trehalose.
  • Examples of the glucosides include alkylglucosides, phenolglucosides, and mustard seed oil glucoside.
  • Examples of the sugar alcohols include D, L-arabite, ribitol, xylitol, D, L-sorbitos, D, L-mannitol, D, L-iditol, D, L-talitol, dulcitol, and allodulcitol.
  • maltitol, obtained by hydrogenating a disaccharide, and a reductant obtained by hydrogenating an oligosaccharide i.e., reduced starch syrup
  • sugar alcohol and saccharose are more preferable.
  • D-sorbitol, saccharose, and reduced starch syrup are even more preferable since they have buffer effect within an appropriate pH range and are inexpensive.
  • nonreducing sugars may be used alone or in combinations of two or more.
  • the content of the nonreducing sugar in the non-silicate developer is preferably 0.1 to 30 wt %, and more preferably 1 to 20 wt %, from the viewpoints of availability and promoting higher concentration.
  • the base combined with the nonreducing sugar(s) may be an alkali agent that has been known so far.
  • alkali agent examples thereof include inorganic alkali agents such as sodium hydroxide, potassium hydroxide, lithium hydroxide, trisodium phosphate, tripotassium phosphate, triammonium phosphate, disodium phosphate, dipotassium phosphate, diammonium phosphate, sodium carbonate, potassium carbonate, ammonium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, ammonium hydrogencarbonate, sodium borate, potassium borate and ammonium borate; and organic alkali agents such as monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine,
  • the bases may be used alone or in combinations of two or more. Among these bases, sodium hydroxide and potassium hydroxide are preferable.
  • a developer containing an alkali-metal salt of a nonreducing sugar as the principal component may be used as the non-silicate developer, replacing the combined use of a nonreducing sugar and a base.
  • an alkaline buffer solution containing a weak acid other than the nonreducing sugar and a strong base may be used in the non-silicate developer.
  • the weak acid preferably has a dissociation constant (pKa) of 10.0 to 13.2, and is selected from the weak acids described in "Ionization Constants of Organic Acids in Aqueous Solution” published by Pergmon Press, and others.
  • suitable examples thereof include alcohols such as 2,2,3,3-tetrafluoropropanol-1 and trifluoroethanol, trichloroethanol; aldehydes such as pyridine-2-aldehyde and pyridine-4-aldehyde; phenolic hydroxyl group-containing compounds such as salicylic acid, 3-hydroxy-2-naphthoic acid, catechol, gallic acid, sulfosalicylic acid, 3,4-dihydroxysulfonic acid, 3,4-dihydroxybenzoic acid, hydroquinone, pyrogallol, o-, m-, and p-cresols, and resorcinol; oximes such as acetoxime, 2-hydroxybenzaldehyde oxime, dimethyl glyoxime, ethanediamide dioxime, and acetophenone oxime; nucleic acid-derived substances such as adenosine, inosine, guanine, cytol
  • surfactants and organic solvents may be added as needed to the developer and replenisher, for improvement or control of developing efficiency, dispersion of development scum, or improvement of the ink compatibility of the image region of a printing plate.
  • the surfactant is preferably an anionic, cationic, nonionic or amphoteric surfactant.
  • a reducer such as hydroquinone, resorcin, sodium or potassium salt of an inorganic acid such as sulfurous acid or bisulfurous acid as well as an organic carboxylic acid, an antifoaming agent, a water softener, or the like may be added to the developer and replenisher as needed.
  • planographic printing plate developed with the developer and replenisher is then post-treated with a rinse solution containing washing water, a surfactant, and the like and with a desensitizing solution containing gum arabic or a starch derivative. These treatments may be used in combination as the post-treatment.
  • the surfactant is preferably an anionic, cationic, nonionic or amphoteric surfactant.
  • hydroquinone, resorcin, a reducing agent such as sodium or potassium salt of an inorganic acid such as sodium or potassium sulfite or bisulfite, an organic carboxylic acid, an antifoam agent, and/or a water softener may be added to the developing and replenishers if needed.
  • the printing plate after processing using the developing and replenishers, is then post-treated with washing water, a rinsing solution containing surfactants and the like, and/or a desensitizing solution containing gum arabic or a starch derivative. These treatments may be used in various combinations as the post-treatment of the printing plate precursor according to the invention.
  • automatic developing machines for the printing plates have become widely used for the purpose of streamlining and standardizing the plate-making processes in the printing-plate and printing industries.
  • These automatic developing machines generally consist of a developing unit and a post-treatment unit, a unit for conveying printing plates and various stock solution tanks, and units for spraying solutions, wherein the exposed printing plates are developed while they are conveyed horizontally and sprayed via spray nozzles with various solutions pumped out of the stock tanks.
  • Another kind of automatic developing system wherein the printing plates are conveyed as they are immersed in treatment solution tanks filled with treating solutions one after another by means of the submerged guide rolls or the like.
  • the plates are processed in the solutions, which are periodically replenished with replenisher according to the number of plates processed and the operating time.
  • a method of essentially using only unused treating solutions i.e., a single-round method, may also be used.
  • the planographic printing plate obtained after the steps of image exposure, development, water washing and/or rinsing, and/or gumming has unnecessary image portions (e.g., film edge spots on the original image film and the like), elimination of the unnecessary image portions is performed.
  • elimination method although the method described for example in Japanese Patent Application Publication ( JP-B) No. 2-13293 wherein an image-elimination solution is applied onto the undesirable image portions and the resulting plate is then washed with water after being left for a certain period; the method described in JP-ANo. 59-174842 , wherein the undesirable image portions are eliminated by irradiation of an activated light through an optical fiber and then the resulting plate is developed, may be also used.
  • the developed planographic printing plate thus obtained may, if desired, be coated with a desensitizing gum before it is sent to the printing process; or the plate is additionally subjected to a baking treatment a planographic printing plate higher in printing durability is desired.
  • the plate is preferably treated before the baking treatments with an affinitizing solution described in JP-B No. 61-2518 JP-B No. 55-28062 , JP-A No. 62-31859 , or JP-A No. 61-159655 .
  • the methods include application of the affinitizing solution onto planographic printing plates with sponges or cotton moistened therewith, application by immersing the printing plate into a bath filled with the affinitizing solution, and application by an automatic coater. Additionally, adjustment of the coating amount for uniformity by using a squeezee or a squeezee roller after application of the affinitizing solution provides more favorable results.
  • the suitable coating amount of the affinitizing solution is generally 0.03 to 0.8 g/m 2 (as dry weight).
  • the planographic printing plate applied with the affinitizing solution is then dried as needed and heated at high temperature in a burning processor (e.g., Burning Processor BP-1300 available from Fuji Photo Film Co.).
  • the temperature and the period of heating vary according to the kind of the components constituting the images, but are preferably in the range of 180 to 300°C for 1 to 20 minutes.
  • planographic printing plate that has been subjected to a baking treatment may then be subjected, if needed, to treatments commonly practiced in the art such as water washing and gumming, but if a surface treatment solution containing a water-soluble polymer compound or the like is used, the so-called desensitizing treatment such as gumming or the like may be eliminated.
  • the planographic printing plate obtained after these treatments is then mounted on an offset printing machine or the like, and it is used for printing numerous sheets of paper.
  • a support was prepared in the steps below using a JIS-A-1050 aluminum plate having a thickness of 0.3 mm.
  • the and mechanical surface roughening was carried out by rotating roller type nylon brushes.
  • the average particle size of the polishing agent was 8 ⁇ m and the maximum particle size was 50 ⁇ m.
  • the material of the nylon brushes was 6-10 nylon and hair length and hair diameters were 45 mm and 0.3 mm, respectively.
  • the nylon brushes were produced by implanting the hairs densely in holes formed in stainless cylinders with a diameter of ⁇ 300 mm. Three rotating brushes were used. Two supporting rollers ( ⁇ 200 mm diameter) were placed in lower parts of the brushes with a separation distance of 300 mm.
  • the brush rollers were pushed until the load of the driving motor for rotating the brushes was increased by 7 kW or more from the load before the brush rollers being pushed against the aluminum sheet.
  • the rotation direction of the brushes was the same as the moving direction of the aluminum sheet.
  • the rotation speed of the brushes was 200 rpm.
  • Etching treatment was carried out by spraying an aqueous NaOH solution (NaOH concentration being 26% by weight and also containing an aluminum ion 6.5% by weight) to the aluminum plate at 70°C, to dissolve the aluminum sheet by an amount of 6 g/m 2 . After that, the aluminum sheet was washed with water by spraying.
  • aqueous NaOH solution NaOH concentration being 26% by weight and also containing an aluminum ion 6.5% by weight
  • the aluminum plate was subjected to a desmutting treatment by spraying an aqueous solution containing 1 wt % nitric acid (additionally containing 0.5 wt % aluminum ion) at a temperature of 30°C, and then washed by spraying water.
  • the aqueous nitric acid solutions used for desmutting was the wastewater obtained in the electrochemical surface-roughening step wherein the aluminum plates were electrochemically scratched in an aqueous nitric acid solution using an alternating electrical current.
  • the aluminum plates were further scratched electrochemically by continuous use of a 60-Hz alternating current.
  • the electrolyte used was an aqueous solution containing 10.5 g/L nitric acid (containing additionally 5 g/L of aluminum ion) at a temperature of 50°C.
  • the electrochemical surface roughening was performed using a trapezoidal alternating current having a trapezoidal waveform with a transition period (TP) from zero to peak currency of 0.8 msec and a duty ratio of 1:1 with a carbon electrode as the counter electrode. Ferrite was used as the auxiliary anode.
  • the electrolytic bath used was that of a radial cell type.
  • the electric current density was 30 A/dm 2 at peak value, and when an aluminum plate is used as the anode, the total amount of electric current applied was 220 C/dm 2 . 5% of the current from the power source was divided and sent to the auxiliary electrode.
  • the aluminum plate was sprayed with a solution containing 26 wt % caustic soda and 6.5 wt % aluminum ion at 32°C to melt the aluminum plate at 0.20 g/m 2 to remove the smut mainly containing aluminum hydroxide, which was generated during the previous electrochemical surface-roughening treatment using an alternating electrical current, and to polish the edge portion by dissolving the edge portions of the pits generated. Subsequently, the aluminum plates were washed by a spray using well water.
  • the aluminum plate was desmutted by spraying an aqueous solution containing 15 wt % nitric acid (containing additionally 4.5 wt % aluminum ion) at a temperature of 30°C, and then washed by a spray using well water.
  • Electrochemical surface roughening treatment was carried out continuously by using 60 Hz AC voltage.
  • the electrolytic solution used in this step was an aqueous solution of hydrochloric acid (the concentration thereof being 7.5 g/L and also containing aluminum ion by 5 g/L) at 35°C.
  • the AC power waveform had a trapezoidal rectangular waveform and a carbon electrode was used as an opposed electrode, to effect the electrochemical surface roughening treatment.
  • Ferrite was used as an auxiliary anode.
  • a radial cell type electrolytic bath was used.
  • the current density was 25 A/dm 2 at the peak value of the current and the total electricity quantity was 50 C/dm 2 when the aluminum sheet was used as an anode.
  • Etching treatment was carried out at 32°C for the aluminum sheet by spraying a solution containing 26 wt. % sodium hydroxide and 6.5 wt. % aluminum ion thereon, to dissolve 0.10 g/m 2 of the aluminum sheet, so as to remove the smut, of which main component is mainly aluminum hydroxide produced during the electrochemical roughening treatment of the surface by using alternating current in the prior step. Further, the edge portions of the pits formed were dissolved to make the edge portions smooth. After that, the aluminum sheet was washed by spraying water spray.
  • Desmut treatment was is carried out by spraying with an aqueous solution of 25% by weight sulfuric acid (containing aluminum ion 0.5% by weight) at 60°C and then washing the resulting aluminum sheet was washed by spraying water spray.
  • the electrolytic solution contained sulfuric acid by 170 g/L (and contained aluminum ion 0.5% by weight). The temperature of the electrolytic solution was 43°C. After Then the aluminum sheet was washed with a water by spraying.
  • the electric current density was about 30 A/dm 2 .
  • Final oxide film thickness was about 2.7 g/m 2 .
  • Support B was prepared by sequentially carrying out the aforementioned steps (a) to (j) but omitting the steps (g), (h) and (i).
  • Respective steps were successively performed except that steps (a), (g), (h) and (i) among the aforementioned steps were omitted, a support was prepared.
  • Respective steps were successively performed except that steps (a), (d), (e) and (f) among the aforementioned steps were omitted, a sum of an electricity amount in a (g) step was adjusted to be 450C/dm 2 to prepare a support.
  • Supports A, B, C and D as obtained above were subsequently subjected to the following hydrophilization treatment and undercoating treatment.
  • An aluminum support obtained by anode oxidation treatment was immersed in a treatment bath containing 1 mass % aqueous solution of No. 3 sodium silicate at a temperature of 30°C for 10 seconds, thereby effecting alkali metal silicate salt treatment (silicate treatment). Thereafter, water washing by spraying using well water was performed. Thereupon, a silicate adhering amount was 3.6 mg/m 2 .
  • An undercoating solution having the following composition was coated on the aluminum support thus obtained after alkali metal silicate salt treatment, and was dried at 80°C for 15 seconds. A covering amount after drying was 15 mg/m 2 .
  • a coating solution for undercoat layer A having the composition described below was applied, using a wire bar, onto the support plate having the undercoat layer obtained as described above (the types of the supports are shown in Table 1 below) and dried in a drying oven at 140°C for 50 seconds to obtain a coating amount of 0.85 g/m 2 .
  • a top-layer coating solution B having the composition described below was applied, using a wire bar, onto the supporting plate having the undercoat layer obtained as described above. After application, the supporting plate was dried at 140°C for 60 seconds to produce the positive planographic printing plate precursor of Examples 1 to 3 and Comparative Example 1 having a total coating amount of 1.07 g/m 2 .
  • a recording layer coating solution C having the composition described below was applied, using a wire bar, onto the support plate with an undercoat layer (the types of supports are shown in Table 1 below) obtained in a manner similar to Example. After application of coating solution C, the supporting plate was dried at 140°C for 60 seconds to produce the positive planographic printing plate precursors of Examples 2 and 3 and Comparative Example 2 having a total coating amount of 1.80 g/m 2 .
  • a recording layer coating solution D having the composition described below was applied, using a wire bar, onto the support plate with an undercoat layer (the types of supports are shown in Table 1 below) obtained in a manner similar to Example 1.
  • the supporting plate was dried at 150°C for 100 seconds to produce the positive planographic printing plate precursors of Examples 4 and 5 and Comparative Example 3 having a total coating amount of 1.40 g/m 2 .
  • a raw image was drawn on each of the positive planographic printing plate precursors obtained in Examples 1 to 5 and Comparative Examples 1 to 3, while the beam intensity wass changed stepwise in a Trendsetter 800 manufactured by Creo Inc. at a drum rotational velocity of 250 rpm, and was developed at a constant liquid temperature of 30°C with a developing period of 12 seconds using a PS Processor LP-940HII manufactured by Fuji Photo Film Co. containing a diluted aqueous solution (1:8) of developer DT-2 manufactured by Fuji Photo Film Co. and a diluted aqueous solution (1:1) of finisher FG-1 manufactured by Fuji Photo Film Co. After development, the plate was then observed with a loupe at a magnification of 50 times, and the exposure beam intensity at which spotty undissolved film was not observed was used as an indicator of sensitivity.
  • a solid image was drawn on each of the positive planographic printing plate precursors obtained in Examples 1 to 5 and Comparative Examples 1 to 3 in a Trendsetter 800 manufactured by Creo Inc. at a beam intensity of 10W and a drum rotational velocity of 250 rpm, and developed by using a PS7 Processor LP-940HII manufactured by Fuji Photo Film Co. containing a diluted aqueous solution (1:9) of developer DT-2R manufactured by Fuji Photo Film Co., which was previously saturated with carbon dioxide gas to an electrical conductivity of 37 mS/cm, and a diluted aqueous solution (1:1) of finisher FG-1 manufactured by Fuji Photo Film Co. at a liquid temperature of 30°C with a developing period of 12 seconds.
  • the solubility of the sulfonium salts used in the Examples and Comparative Examples was determined as follows: 50 ml of an aqueous 0.1 mol/L NaOH solution was placed in a transparent glass bottle under the condition of 25°C and 1 atm; then, 50 mg of a sulfonium salt was added thereto and the mixture was stirred for 5 minutes at 25°C while the bottle was sealed; and the solubility was evaluated. If the sulfonium salt was completely dissolved, 50 mg of additional sulfonium salt was added and the mixture was stirred for 5 minutes, and the solubility was evaluated once again.
  • the number (No.) of the sulfonium salt shown in Table 1 is the number allocated to the specific sulfonium salt in the Examples above.
  • planographic printing plate precursors of Examples 1 to 5 having a recording layer containing a specific sulfonium salt according to the present invention has superior sensitivity, and no development scum was generated.
  • planographic printing plate precursors (of Comparative Examples 1 to 3) having a recording layer containing a comparative sulfonium salt having a solubility outside the preferable range of solubility according to the present invention had either lower sensitivity or generated a greater amount of development scum.

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Thermal Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials For Photolithography (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
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  • Formation Of Insulating Films (AREA)
  • Electroluminescent Light Sources (AREA)

Claims (11)

  1. Précurseur de plaque d'impression planographique comprenant :
    un support ; et
    une couche d'enregistrement sur le support comprenant un sel de sulfonium (A), une résine soluble dans l'alcali (B) et un produit absorbant l'infrarouge (C) ;
    dans lequel le cation du sel de sulfonium (A) à trois groupes phényle, au moins un des trois groupes phényle étant substitué par un groupe -OH, et
    le sel de sulfonium (A) a une solubilité d'au moins 25 mg/ml dans une solution aqueuse de NaOH à 0,1 mol/l, la solution étant à 25 °C et sous une pression de 1 atm.
  2. Précurseur de plaque d'impression planographique selon la revendication 1, dans lequel au moins deux des trois groupes phényle du sel de sulfonium (A) sont substitué par un groupe -OH.
  3. Précurseur de plaque d'impression planographique selon la revendication 2, dans lequel chacun des trois groupes phényle du sel de sulfonium (A) est substitué par un groupe -OH.
  4. Précurseur de plaque d'impression planographique selon la revendication 1, dans lequel au moins un des trois groupes phényle du sel de sulfonium (A) a un substituant qui n'est pas un groupe soluble dans l'alcali.
  5. Précurseur de plaque d'impression planographique selon la revendication 4, dans lequel le substituant qui n'est pas un groupe soluble dans l'alcali est sélectionné à partir du groupe constitué par un atome d'halogène, un groupe nitro, un groupe alkyle ayant 12 atomes de carbone ou moins, un groupe alcoxy ayant 12 atomes de carbone ou moins et un groupe aryloxy ayant 12 atomes de carbone ou moins.
  6. Précurseur de plaque d'impression planographique selon l'une quelconque des revendications précédentes, dans lequel l'anion du sel de sulfonium (A) est un groupe qui est une base conjuguée d'un acide fort.
  7. Précurseur de plaque d'impression planographique selon la revendication 6, dans lequel le groupe qui est une base conjuguée d'un acide fort est un résidu obtenu à partir d'un ion d'halogène, d'un acide sulfonique, d'un acide carboxylique ou d'un acide inorganique.
  8. Précurseur de plaque d'impression planographique selon la revendication 7, dans lequel le résidu obtenu à partir d'un acide inorganique est un ion d'halogénure, HSO4 - ou un ion de complexe contenant un halogène.
  9. Précurseur de plaque d'impression planographique selon la revendication 8, dans lequel le résidu obtenu à partir d'un acide inorganique est obtenu à partir d'un acide inorganique contenant un atome de fluor.
  10. Précurseur de plaque d'impression planographique selon la revendication 6, dans lequel le groupe qui est une base conjuguée d'un acide fort a un pKa inférieur à 5.
  11. Précurseur de plaque d'impression planographique selon la revendication 6, dans lequel le groupe qui est une base conjuguée d'un acide fort contient des groupes acides multiples.
EP06002128A 2005-02-09 2006-02-02 Précurseur de plaque d'impression planographique Active EP1690685B1 (fr)

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DE602006006233D1 (de) 2009-05-28
ATE428559T1 (de) 2009-05-15
JP4474296B2 (ja) 2010-06-02
EP1690685A2 (fr) 2006-08-16
EP1690685A3 (fr) 2007-03-28

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