EP2080616B1 - Flachdruckplattenvorläufer - Google Patents

Flachdruckplattenvorläufer

Info

Publication number
EP2080616B1
EP2080616B1 EP09150845.7A EP09150845A EP2080616B1 EP 2080616 B1 EP2080616 B1 EP 2080616B1 EP 09150845 A EP09150845 A EP 09150845A EP 2080616 B1 EP2080616 B1 EP 2080616B1
Authority
EP
European Patent Office
Prior art keywords
printing plate
polymer
acid
recording layer
planographic printing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Not-in-force
Application number
EP09150845.7A
Other languages
English (en)
French (fr)
Other versions
EP2080616A1 (de
Inventor
Ikuo Kawauchi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Corp
Original Assignee
Fujifilm Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fujifilm Corp filed Critical Fujifilm Corp
Publication of EP2080616A1 publication Critical patent/EP2080616A1/de
Application granted granted Critical
Publication of EP2080616B1 publication Critical patent/EP2080616B1/de
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

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
    • 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
    • B41C2210/14—Multiple imaging layers
    • 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 present invention relates to a planographic printing plate precursor. More specifically, the invention relates to an infrared-laser-applicable planographic printing plate precursor from which a printing plate can be directly formed based on digital signals from a computer or the like.
  • Materials which can be used for positive planographic printing plate precursors applicable for infrared lasers include, as essential components, a binder resin soluble in an aqueous alkaline solution (hereinafter referred to where appropriate as an "alkali-soluble resin"), and an infrared dye which absorbs light to generate heat.
  • the infrared dye interacts with the binder resin in its unexposed portions (image portions) so as to function as a dissolution inhibitor which can substantially reduce the solubility of the binder resin.
  • image portions image portions
  • dissolution inhibitor which can substantially reduce the solubility of the binder resin.
  • interaction of the infrared dye with the binder resin is weakened by the heat generated. Consequently, an exposed portion can turn into a state in which it can be dissolved in an alkaline developer, so that an image is formed thereon and a planographic printing plate is produced.
  • the plate precursor when using an infrared-laser-applicable positive planographic printing plate precursor, if the surface state of the unexposed portions of the plate precursor is slightly changed by human finger touching the surface or some other action, the affected unexposed portions (image portions) are dissolved by development to generate marks like scars. As a result, the plate precursor has problems in that the printing durability thereof deteriorates and the ink-acceptability thereof worsens.
  • the positive planographic printing plate material used for plate-making by exposure to UV light includes a binder resin soluble in an aqueous alkali solution, an onium salt and a quinone diazide compound as essential ingredients.
  • the onium salt and quinone diazide compound act, in light-unexposed regions (image regions), as a dissolution inhibitor by interaction with the binder resin.
  • non-image regions In light-exposed regions (non-image regions), on the other hand, they act as a dissolution accelerator by generating an acid upon decomposition by light. That is, the onium salt and quinone diazide compound play two roles, that is, the role of dissolution inhibitor and the role of acid generator.
  • the infrared dye functions only as a dissolution inhibitor of unexposed portions (image portions), and does not promote the dissolution of exposed portions (non-image portions). Therefore, in order to make distinctive the difference in solubility between the unexposed portion and the exposed portion in the a positive planographic printing plate precursor for infrared laser, it is inevitable that a material which already has a high solubility in an alkali developing solution is used as the binder resin. There is therefore the case that the state of the plate material before developed becomes unstable.
  • an ink-receptive recording layer of such a planographic printing plate precursor is formed on a hydrophilic support, and as a result, adhesion of the recording layer at the interface of the support may become unstable, which may affect printing durability of an unexposed area (image area) of a planographic printing plate formed therefrom, and in particular, reproducibility of images having a small image area, such as thin lines or dots, may be significantly affected.
  • image area image area
  • reproducibility of images having a small image area such as thin lines or dots
  • a planographic printing plate precursor having a recording layer having a multilayer structure has been proposed in which a lower layer that contains a polymer having a structural unit having -NH- and -SO 2 - groups in a side chain thereof and a heat-sensitive upper layer that contains a phenolic resin and an infrared absorbing agent are provided on a hydrophilic substrate in this order (see, for example, EP-A1 No. 1826001 ).
  • EP-A-1 826 021 discloses a positive-working lithographic printing plate precursor including two recording layers, but only the upper of these includes an infrared absorber.
  • EP-A-2042308 prior art according to Article 54(3) EPC only, discloses a planographic printing plate precursor comprising:
  • the recording layer having such a multilayer structure necessitates selecting resins having properties which are different from each other as resins used in individual layers making up the recording layer, which causes a problem in that interaction between them is weakened or a problem in that the unexposed portions of the lower layer cause elution from the interface with a developer under development because of high susceptibility of the lower layer to development, or what is called the side-edge problem.
  • An object of the present invention is to provides a positive planographic printing plate precursor excellent in image reproducibility of images having a small image area formed by high resolution exposure as well as printing durability and chemical resistance.
  • planographic printing plate precursor comprising:
  • R 1 represents a hydrogen atom or an alkyl group
  • Z represents -O- or NR 2
  • R 2 represents a hydrogen atom, an alkyl group, an alkenyl group, or a alkynyl group
  • Ar 1 and Ar 2 each independently represent an aromatic group; at least one of Ar 1 and Ar 2 is a hetero aromatic group; and a and b each independently denote 0 or 1.
  • R 1 may further have a substituent.
  • R 2 may further have a substituent.
  • Ar 1 may further have a substituent.
  • Ar 2 may further have a substituent.
  • the positive recording layer nearest to a support is hereinafter referred to as a "lower layer” or a “lower recording layer” as necessary.
  • planographic printing plate precursor of the invention may be provided to the planographic printing plate precursor of the invention in addition to the plurality of the positive recording layers as long as the effect of the invention is not hindered.
  • the dispersion phase formed by a resin in the recording layer can be formed by, for example, (1) using a plural kinds of resins that are incompatible with each other in combination, or (2) dispersing, in a resin constituting the matrix phase, the resin constituting the dispersion phase in granular form such as microcapsule or latex form.
  • the planographic printing plate precursor of the invention employs a system utilizing change of solubility of the recording layer to an alkaline water. Therefore, in a preferable embodiment, a resin used in the positive recording layer has a water-insoluble and alkaline water-soluble resin.
  • the method (1) which is a method including forming a dispersion phase and a matrix phase (a dispersion medium) by using a plural kind of resins that are incompatible with each other in combination, is preferable from the standpoint of ease of production.
  • the plural kind of resins may be those which are incompatible, or may be those which can be dissolved uniformly in a coating solvent and form a dispersion phase along with the removal of the solvent when forming the recording layer.
  • At least one of the resins contained in the lower recording layer is a specific polymer in the present invention.
  • the specific polymer is preferably used as a resin which is included in a matrix phase (dispersion medium).
  • the rate of dissolution of the resin contained in the dispersion phase with respect to an alkaline aqueous solution is preferably slower than that of the resin included in the matrix phase.
  • a polymer which is included in the dispersion phase in the invention can be selected from resins described hereinafter. Among those resins, a novolak resin is particularly preferable as the polymer which contained in the dispersion phase.
  • the maximum major axis of the dispersion phase is preferably from 0.1 ⁇ m to 0.8 ⁇ m, and the average major axis of the dispersion phase is preferably from 0.05 ⁇ m to 0.6 ⁇ m.
  • the size of the dispersion phase can be evaluated by cutting the recording layer with a microtome or the like to give sections of the recording layer, then making the sections electroconductive, taking a photograph thereof with a scanning electron microscope (SEM) and evaluating the size of the circular or elliptical dispersion phase by an image analyzer.
  • SEM scanning electron microscope
  • the resin matrix phase in the lower recording layer of the planographic printing plate precursor of the invention is provided with a dispersion phase, the solubility of which to an aqueous alkali solution is increased by heat or light.
  • this configuration results in formation of paths by which an aqueous alkali solution permeates into the matrix phase, whereby accelerates the dissolution of the alkali-soluble resin matrix phase in the lower recording layer to the aqueous alkali solution.
  • the solubility of the dispersion phase to an aqueous alkali solution is lower than that of the resin which configurates the matrix phase.
  • the permeation of an aqueous alkali solution into the resin matrix phase in the lower recording layer can be efficiently suppressed so as to prevent the image regions from being damaged by the aqueous alkali solution.
  • the image regions have excellent adherence to the support. It is expected that these conditions result in the excellent image reproducibility as well as printing durability and chemical resistance of the planographic printing plate precursor of the invention. Further, since the specific polymer, that is necessarily contained in the lower recording layer, exhibits remarkable solubilization resistance against organic solvents, the lower recording layer is expected as being able to avoid being damaged.
  • planographic printing plate precursor of the invention is particularly useful in formation of a high definition image using a high resolution exposure apparatus, for example, PT-R SERIES (trade name, manufactured by Dainippon Screen Mfg. Co., Ltd.), TRENDSETTER UHR (trade name, manufactured by KGC) and is also useful in formation of a high definition image using, for example, a FM screen which increases its use with recent CTP application, and can preferably be used in image formation using commercially available FM screens such as STACCATO (trade name, manufactured by KGC), FAIRDOT, RANDOT (both trade names, manufactured by Dainippon Screen Mfg. Co., Ltd.), Co-Re SCREEN or TAFFETA (both are trade names, manufactured by FUJIFILM Corporation).
  • a high resolution exposure apparatus for example, PT-R SERIES (trade name, manufactured by Dainippon Screen Mfg. Co., Ltd.), TRENDSETTER UHR (trade name, manufactured by KGC)
  • FM screen which increases its use with recent
  • a positive planographic printing plate precursor excellent in image reproducibility of a high definition image as well as printing durability and chemical resistance. Accordingly, in particular, according to an aspect of the present invention, it is possible to improve the stability in plate making when forming a high definition image. Further, it is also possible to obtain favorable printing durability of high definition image portions.
  • the scope of the term "high definition images" includes an FM screen image whose use has been increasing with recent CTP application.
  • Figure 1 is a graph of one example of an alternating current waveform used for electrochemical surface roughening treatment applied for the preparation of a support of a planographic printing plate precursor in the following EXAMPLES.
  • Figure 2 is a side view of one example of a radial-type cell used for the electrochemical surface roughening treatment with the alternating current waveform used for the preparation of a support of a planographic printing plate precursor in the following EXAMPLES.
  • the planographic printing plate precursor of the invention includes: a support; and two or more positive recording layers each containing at least a resin and an infrared absorber, each of the layers having a solubility with respect to an aqueous alkali solution that is increased by exposure to infrared laser light, wherein: of the two or more positive recording layers, a positive recording layer that is nearest to the support contains at least two resins; one of the at least two resins is a polymer ("specific polymer") having at least one structural unit selected from the group consisting of a structural unit represented by the following Formula (I) and a structural unit represented by the following Formula (II); at least one of the at least two resins is included in a dispersion phase that is dispersed in a matrix phase; and the matrix phase serves as a dispersion medium and includes at least one of the other of the at least two resins.
  • the rate of dissolution with respect to an alkaline aqueous solution of the resin included in the dispersion phase is slower than that of the
  • R 1 represents a hydrogen atom or an alkyl group
  • Z represents -O- or NR 2
  • R 2 represents a hydrogen atom, an alkyl group, an alkenyl group, or a alkynyl group
  • Ar 1 and Ar 2 each independently represent an aromatic group; at least one of Ar 1 and Ar 2 is a hetero aromatic group; and a and b each independently denote 0 or 1.
  • R 1 may further have a substituent.
  • R 2 may further have a substituent.
  • Ar 1 may further have a substituent.
  • Ar 2 may further have a substituent.
  • Embodiment (1) a dispersion phase is formed in a matrix phase, i.e., a dispersion medium, using at least two resins (polymer compounds) which are incompatible with each other. A dispersion phase formed thereby is formed of a material which is incompatible with a material which forms the dispersion medium.
  • Embodiment (2) a dispersion phase containing given components is formed using a microcapsule or a latex, and the dispersion phase is then introduced into a polymer binder, i.e., a rein matrix phase. A dissolution inhibitor and/or an infrared absorber can be added to the dispersion phase if necessary.
  • At least one of the two or more incompatible polymer compounds is a polymer insoluble in water and soluble in an aqueous alkali solution, and this polymer is preferably the polymer compound included in the matrix phase.
  • the polymer insoluble in water and soluble in an aqueous alkali solution is preferably a specific polymer.
  • incompatible means that a combination of the two or more polymers does not outwardly appear as a one-phase solid or liquid, this being confirmed by suitably processing of sections of the recording layer and visually observing the sections or taking photographs of the sections with a scanning electron microscope and observing them.
  • Examples of the polymer compound used in the combination of the at least two polymers that are incompatible with each other include a urethane polymer compound, an acrylic polymer compound, a styrene polymer compound, a novolak resin, a diazo resin, an amide polymer compound, and a polyether compound.
  • Examples of the preferable combination include: a combination of an acrylic polymer compound and a urethane polymer compound; a combination of an acrylic or urethane polymer compound and a diazo resin; and a combination of a novolak resin and a urethane polymer compound.
  • a combination containing a urethane polymer compound is preferable from the standpoint that it is relatively free from being damaged at the time of development.
  • a dispersion phase is formed in the resin matrix phase, and an amount of the infrared absorber in the dispersion phase becomes large.
  • a polymer which shows a stronger interaction due to hydrogen bonding, ionic properties etc. easily forms spheres or flat spheres in the binder.
  • Such localization occurs because when an infrared absorber is present in a dispersion phase, the infrared absorber, which is generally ionic or a coordination complex, tends to be easily incorporated into the polymer compound showing the stronger interaction in the binder.
  • the initiator When an acid generator or a radical generator (polymerization initiator) is made to coexist, the initiator usually has a group having high polarity such as an onium salt structure, triazine or sulfonate ester, and, similar to the infrared absorber, is easily incorporated into the dispersion phase.
  • sea-island structure a structure in which a dispersion phase is formed in a polymer matrix phase as the dispersion medium.
  • the sea-island structure can be observed and evaluated in the following manner: a section of the recording layer obtained by cutting the planographic printing plate precursor by a microtome or the like is made to have conductivity and then a photograph of an image of the section is taken by a scanning electron microscope (SEM) to analyze the size of a circular or elliptic dispersion phase by using an image analyzer.
  • SEM scanning electron microscope
  • the section of the recording layer can be subjected to, for example, etching with solvent and then a photograph of the section can be taken according to the method described in, for example, "Polymer Alloy and Polymer Blend" (L. A. UTRACKI, translated by Toshio NISHI, Tokyo Kagaku Dojzin), the disclosure of which is incorporated by reference herein, to thereby obtain a highly distinct image.
  • Polymer Alloy and Polymer Blend L. A. UTRACKI, translated by Toshio NISHI, Tokyo Kagaku Dojzin
  • a size of the dispersion phase present in the polymer binder phase depends on a coating solvent system, drying conditions after application, and the like.
  • a dispersion phase having the maximum major axis length of 0.8 ⁇ m or less, which is preferably 0.6 ⁇ m or less, and an average major axis length of 0.6 ⁇ m or less, which is preferably 0.5 ⁇ m or less, can be formed by controlling those conditions. In this case, it is preferable that the maximum major axis length and the average major axis length are small.
  • the lower limit of the size of a dispersion phase is not particularly limited.
  • the maximum major axis length is about 0.1 ⁇ m, and the average major axis diameter is about 0.05 ⁇ m.
  • the "major axis length" is obtained by subjecting a dispersion phase to image analysis as described above, and means a diameter when a particle of the dispersion phase is circle, or means a major axis length when a particle of the dispersion phase is ellipse.
  • At least one resin among one or more resins contained in the lower recording layer is required to be the specific polymer in the planographic printing plate precursor of the present invention.
  • the specific polymer is preferably contained as a resin which configurates a resin matrix phase in the lower recording layer.
  • the specific polymer is described below in detail.
  • the specific polymer in the invention is a polymer having at least one selected from a group consisting of a structural unit represented by the following Formula (I) and a structural unit represented by the following Formula (II).
  • R 1 represents a hydrogen atom or an alkyl group
  • Z represents -O- or -NR 2 wherein R 2 represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group
  • Ar 1 and Ar 2 each independently represent an aromatic group, provided that at least either of them is a hetero aromatic group
  • a and b each independently represent 0 or 1.
  • R 1 represents a hydrogen atom or an alkyl group, wherein the alkyl group is a substituted or unsubstituted alkyl group, and is preferably an unsubstituted alkyl group.
  • alkyl group represented by R 1 include lower alkyl groups, such as a methyl group, an ethyl group, a propyl group and a butyl group. It is preferable that R 1 is a hydrogen atom or a methyl group.
  • Z represents -O- or -NR 2 -, and is preferably -NR 2 -.
  • R 2 represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted alkynyl group.
  • R 2 is preferably a hydrogen atom or an unsubstituted alkyl group, and more preferably a hydrogen atom.
  • a and b each independently represent 0 or 1.
  • the case where a is 0 and b is 1 is a is preferable, the case where both a and b are 0 is more preferable, and the case where both a and b are 1 is still more preferable.
  • Z is preferably O.
  • Z is preferably NR 2 , and in this case R 2 is preferably a hydrogen atom.
  • Ar 1 and Ar 2 each independently represent an aromatic group, and at least either of them is a hetero aromatic group.
  • Ar 1 is a divalent aromatic group
  • Ar 2 is a monovalent aromatic group.
  • These aromatic groups each are a substituent formed by substituting one or two linkage groups for one or two hydrogen atoms as constituents of the aromatic ring.
  • Such an aromatic ring may be selected from among hydrocarbon aromatic rings including benzene, naphthalene and anthracene, or it may be selected from among hetero aromatic rings including furan, thiophene, pyrrole, imidazole, 1,2,3-triazole, 1,2,4-triazole, tetrazole, oxazole, isooxazole, thiazole, isothiazole, thiadiazole, oxadiazole, pyridine, pyridazine, pyrimidine, pyrazine, 1,3,5-triazine, 1,2,4-triazine and 1,2,3-triazine.
  • the aromatic ring may be a fused ring formed by fusing two or more of those rings together, such as benzofuran, benzothiophene, indole, indazole, benzoxazole, quinoline, quinazoline, benzimidazole or benzotriazole.
  • aromatic or hetero aromatic groups may further have a substituent, and examples of substituents which can be introduced into them include an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, a heteroaryl group, a hydroxyl group, -SH, a carboxylic acid group or alkyl esters thereof, a sulfonic acid group and alkyl esters thereof, a phosphinic acid group and alkyl esters thereof, an amino group, a sulfonamide group, an amido group, a nitro group, a halogen atom, and substituents formed by two or more of these groups being linked together.
  • substituents may be substituents further having any of the substituents as recited above.
  • Ar 2 is preferably a hetero aromatic group which may have a substituent, more preferably a nitrogen-containing hetero aromatic ring selected from pyridine, pyridazine, pyrimidine, pyrazine, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole, oxazole, isooxazole, thiazole, isothiazole, thiadiazole, oxadiazole or the like.
  • a nitrogen-containing hetero aromatic ring selected from pyridine, pyridazine, pyrimidine, pyrazine, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole, oxazole, isooxazole, thiazole, isothiazole, thiadiazole, oxadiazole or the like.
  • Examples of a monomer capable of forming the structural unit represented by Formula (I) or Formula (II) are illustrated below, but these examples should not be construed as limiting the scope of the invention.
  • monomers having the linkage group -SO 2 -NH- when viewed from the main chain side are those which can be converted into the structural units represented by Formula (I)
  • monomers having the linkage group -NH-SO 2 - are those which can be converted into the structural units represented by Formula (I)
  • monomers having the linkage group -NH-SO 2 - are those which can be converted into the structural units represented by Formula (II).
  • the specific polymer is an alkali-soluble polymer containing structural units represented by Formula (I) or Formula (II), and the structural units contained in the specific polymer and represented by Formula (I) or Formula (II) may be of only one kind or a combination of two or more kinds.
  • the content of structural units represented by Formula (I) or Formula (II) is preferably from 10 to 100 mole%, more preferably from 20 to 90 mole%, still more preferably from 30 to 80 mole%, particularly preferably from 30 to 70 mole%.
  • the specific polymer containing those structural units may be a copolymer containing other structural units in addition to the structural units represented by Formula (I) or Formula (II).
  • the other structural units include structural units derived from hydrophobic monomers having substituents like alkyl or aryl groups in their respective side chain structures, and those derived from hydrophilic monomers having substituents like acidic, amido, hydroxyl or ethylene oxide groups in their respective side chain structures.
  • monomers to be copolymerized can be selected from those monomers as appropriate according to the intended purpose, the selection of monomer species for copolymerization may be made within the range of producing no negative effect on alkali solubility of the specific polymer.
  • Examples of other copolymerization components usable in synthesis of the specific polymer according to the invention include (meth)acrylamide, N-substituted (meth)acrylamides, N-substituted maleimides, (meth)acrylic esters, (meth)acrylic esters having polyoxyethylene chains, 2-hydroxyethyl (meth)acrylate, styrene, styrenesulfonic acid, o-, p- or m-vinylbenzene acids, vinylpyridine, N-vinylcaprolactam, N-vinylpyrrolidine, (meth)acrylic acid, itaconic acid, maleic acid, glycidyl (meth)acrylate, hydrolyzable vinyl acetate and vinylphosphonic acid.
  • N-benzyl(meth)acrylamide and (meth)acrylic acid can be used as preferred copolymerization components.
  • the number average molecular weight (Mn) of the specific polymer is preferably from 10,000 to 500,000, more preferably from 10,000 to 200,000, still more preferably from 10,000 to 100,000.
  • the weight average molecular weight (Mw) is preferably from 10,000 to 1000,000, more preferably from 20,000 to 500,000, still more preferably from 20,000 to 200,000.
  • Copolymer (21) Copolymer (15)-modified compound, wherein the structural unit derived from N-(4-hydroxy-3,5-dimethyl-benzylacrylamide) is substituted for the structural unit derived from acrylic acid in Copolymer (15).
  • the specific polymer content in the lower recording layer is preferably 40 to 95 % by mass , more preferably 50 to 95 % by mass, of the total solid content in the lower recording layer.
  • the content ratio by mass of the specific polymer to a resin included in the dispersion phase is preferably from 90:10 to 60:40.
  • the positive recording layer contains at least a resin (namely, a polymer compound insoluble in water and soluble in an aqueous alkali solution) and an infrared absorber (namely, a compound which suppresses the alkali solubility of the resin).
  • a resin namely, a polymer compound insoluble in water and soluble in an aqueous alkali solution
  • an infrared absorber namely, a compound which suppresses the alkali solubility of the resin.
  • the water-insoluble and aqueous alkali-soluble polymer compound (hereinafter referred to as an "alkali-soluble polymer" as required) which is used in plural positive recording layers includes homopolymers having an acidic group on a main chain and/or a side chain thereof, copolymers having an acidic group on a main chain and/or a side chain thereof, and mixtures of these polymers.
  • the polymer layer according to the invention therefore has the characteristics that it is dissolved when being brought into contact with an alkali developing solution.
  • the scope of the alkali-soluble polymer contained in the lower recording layer in the planographic printing plate precursor of the invention includes the specific polymer.
  • any known alkali-soluble polymer may be used as the alkali-soluble polymer to be used in the lower recording layer and other recording layers (hereinafter referred to as an upper recording layer as required) in the invention without any particular limitation, while the alkali-soluble polymer is preferably a polymer compound having one functional group selected from (1) a phenolic hydroxyl group, (2) a sulfonamide group and (3) an active imide group in its molecule.
  • the following compounds are given as examples, while these examples are not intended to be limiting of the invention.
  • polymer compounds having phenolic hydroxyl group examples include novolak resin such as condensation polymers of phenol and formaldehyde; condensation polymers of m-cresol and formaldehyde, condensation polymers of p-cresol and formaldehyde, condensation polymers of m-/p-mixed cresol and formaldehyde, and condensation polymers of phenol/cresol (m-, p-, or m-/p-mixture) and formaldehyde; and condensation copolymers of pyrogallol and acetone.
  • the polymer compound having a phenolic hydroxyl group it is preferable to use polymer compounds having a phenolic hydroxyl group at their side chains besides the above compounds.
  • Examples of the polymer compound having a phenolic hydroxyl group at its side chain include polymer compounds obtained by homopolymerizing a polymerizable monomer comprising a low-molecular compound having one or more phenolic hydroxyl groups and one or more polymerizable unsaturated bonds or copolymerizing this monomer with other polymerizable monomers.
  • Examples of the polymerizable monomer having a phenolic hydroxyl group include acrylamides, methacrylamides, acrylate esters and methacrylate esters each having a phenolic hydroxyl group, and hydroxystyrenes.
  • polymerizable monomer which may be preferably used include 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-hydroxyphenylacrylate, m-hydroxyphenylacrylate, p-hydroxyphenylacrylate, o-hydroxyphenylmethacrylate, m-hydroxyphenylmethacrylate, p-hydroxyphenylmethacrylate, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, 2-(2-hydroxyphenyl)ethylacrylate, 2-(3-hydroxyphenyl)ethylacrylate, 2-(4-hydroxyphenyl)ethylacrylate, 2-(2-hydroxyphenyl)ethylmethacrylate
  • condensation polymers of phenols having an alkyl group having 3 to 8 carbon atoms as a substituent and formaldehyde such as a t-butylphenol formaldehyde resin and octylphenol formaldehyde resin as described in the specification of U.S. Patent No. 4,123,279 may be used together.
  • Examples of the alkali-soluble polymer compound having a sulfonamide group include polymer compounds obtained by homopolymerizing polymerizable monomers having a sulfonamide group or by copolymerizing the monomer with other polymerizable monomers.
  • Examples of the polymerizable monomer having a sulfonamide group include polymerizable monomers comprising a low-molecular compound having, in one molecule thereof, one or more sulfonamide groups -NH-SO 2 - in which at least one hydrogen atom is added to a nitrogen atom and one or more polymerizable unsaturated bonds.
  • low-molecular compounds having an acryloyl group, allyl group or vinyloxy group and a substituted or monosubstituted aminosulfonyl group or substituted sulfonylimino group are preferable.
  • the alkali-soluble polymer compound having an active imide group is preferably those having an active imide group in its molecule.
  • the polymer compound include polymer compounds obtained by homopolymerizing a polymerizable monomer comprising a low-molecular compound having one or more active imide groups and one or more polymerizable unsaturated bonds or copolymerizing this monomer with other polymerizable monomers.
  • a compound specifically, N-(p-toluenesulfonyl)methacrylamide, N-(p-toluenesulfonyl)acrylamide and the like are preferably used.
  • alkali-soluble polymer compound of the invention polymer compounds obtained by polymerizing two or more types among the polymerizable monomers having a phenolic hydroxyl group, polymerizable monomers having a sulfonamide group and polymerizable monomers having an active imide group, or polymer compounds obtained by copolymerizing these two or more polymerizable monomers with other polymerizable monomers are preferably used.
  • the ratio by weight of these components to be compounded is preferably in a range from 50:50 to 5:95 and particularly preferably in a range from 40:60 to 10:90.
  • the alkali-soluble polymer is a copolymer of the polymerizable monomer having a phenolic hydroxyl group, polymerizable monomer having a sulfonamide group or polymerizable monomer having an active imide group and other polymerizable monomers in the invention, it is preferable to contain a monomer imparting alkali-solubility in an amount of 10 mol% or more and more preferably 20 mol% or more in view of improving the solubility to an alkali solution and the development latitude of the precursor.
  • Examples of the monomer component to be copolymerized with the polymerizable monomer having a phenolic hydroxyl group, the polymerizable monomer having a sulfonamide group and the polymerizable monomer having an active imide group may include, though not particularly limited to, compounds represented by the following (ml) to (m12).
  • 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.
  • the alkali-soluble polymer compound preferably has a phenolic hydroxyl group, in terms of the excellent image formability by exposure by infrared laser.
  • the alkali-soluble polymer compound having a phenolic hydroxyl group include condensed copolymers of phenol and formaldehyde comprising an alkyl group having 3 to 8 carbon atoms as a substitute, such as tert-butylphenol formaldehyde resin and octylphenol formaldehyde resin described in US Patent No. 4,123,279 .
  • a method of copolymerizing the aqueous alkali-soluble polymer compound for example, a conventionally known graft copolymerization method, block copolymerization method or random copolymerization method may be used.
  • a resin having a phenolic hydroxyl group is desirable in the point that it develops strong hydrogen bonding characteristics in an unexposed portion whereas a part of hydrogen bonds are released with ease in an exposed portion.
  • the alkali-soluble polymer is more preferably a novolac resin.
  • the alkali-soluble resin preferably has a weight average molecular weight of 500 to 20,000 and a number average molecular weight of 200 to 10,000.
  • a preferable method of forming a dispersion phase in the lower recording layer will be described.
  • selection of a coating solvent is an important factor in order that the dispersion phase forms a sea-island structure in the lower recording layer with a maximum major axis of 0.8 ⁇ m or less and average major axis of 0.6 ⁇ m or less.
  • a sea-island structure having the target size can be formed.
  • a clear mechanism has not been found out as to the reason why the size of the dispersion phase is reduced or varied by the selection of a coating solvent system.
  • a ketone solvent such as cyclohexanone or methyl ethyl ketone, alcohol solvent such as methanol, ethanol, propanol or 1-methoxy-2-propanol, cellosolve solvent such as ethylene glycol monomethyl ether, lactone solvent such as ⁇ -butyrolactone, sulfoxide such as dimethyl sulfoxide or sulfolane, halogen solvent such as ethylene dichloride, acetate solvent such as 2-methoxyethyl acetate or 1-methoxy-2-propyl acetate, ether solvent such as dimethoxyethane, ester solvent such as methyl lactate or ethyl lactate, amide solvent such as N,N-dimethoxyacetamide or N,N-dimethylformamide, pyrrolidone solvent such as N-
  • methyl ethyl ketone, 1-methoxy-2-propanol, ethylene glycol monomethyl ether, ⁇ -butyrolactone and dimethyl sulfoxide are preferable. These solvents may be used either singly or by mixing two or more.
  • the condition under which a coating layer that has not yet been dried (after the photosensitive coating liquid is applied) is dried is known as an important factor to make the dispersion phase of the sea-island structure in the lower recording layer to have a specified size.
  • the descriptions in JP-A No. 9-90610 may be adopted as a reference for the production of such a sea-island structure.
  • the polymer compound used to form the dispersion phase in the case of forming the polymer matrix phase and the dispersion phase by using the two or more polymer compounds incompatible with each other are shown below.
  • Examples of the polymer compound which can be preferably used for forming the dispersion phase in the invention include copolymers having a structural unit derived from at least one of monomers corresponding to any one of the following (1) to (5), urethane polymer compounds, novolac resins, diazo resins and polyethers. Among these, novolak resin is particularly preferable as the polymer compound used for forming the dispersion phase.
  • Examples of the above structural unit include acrylamides, methacrylamides, acrylate esters and methacrylate esters having an aromatic hydroxyl group. Specific examples these compounds include N-(4-hydroxyphenyl)acrylamide or N-(4-hydroxyphenyl)methacrylamide, o-, p- or m-hydroxyphenylacrylate or methacrylate and 2-hydroxyethylmethacrylate.
  • Examples of the above structural unit also include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid anhydride and itaconic acid.
  • Examples of the above structural unit also include low-molecular compounds having at least one sulfonamide group in which at least one hydrogen atom is bonded to a nitrogen atom and at least one polymerizable unsaturated bond, for example, compounds represented by the following Formulae (i) to (v).
  • 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 group, a cycloalkylene group, an arylene group or an aralkylene group which has 1 to 12 carbon atoms and may have a substituent;
  • R 3 , R 7 and R 13 each independently represent a hydrogen atom, or an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group which has 1 to 12 carbon atoms and may have a substituent;
  • R 6 and R 17 each independently represent an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group which has 1 to 12 carbon atoms and may have a substituent;
  • R 8 , R 10 and R 14 each independently represent a hydrogen
  • Specific examples of the compounds represented by any one of Formulae (i) to (v) include m-aminosulfonylphenyl methacrylate, N-(p-aminosulfonylphenyl)methacrylamide and N-(p-aminosulfonylphenyl)acrylamide.
  • Examples of the above structural unit also include low-molecular compounds containing at least one active imino group represented by the following Formula (vi) and at least one polymerizable unsaturated bond, for example, N-(p-toluenesulfonyl)methacrylamide and N-(p-toluenesulfonyl)acrylamide.
  • Examples of the above structural unit also include styrene compounds, vinyl acetate and vinyl alcohol, for example, o-, m- or p-hydroxystyrene, styrene p-sulfonate and o-, m- or p-carboxylstyrene.
  • the monomers corresponding to any one of the above (1) to (5) may be used either singly or in combinations of two or more. Copolymers obtained by combining any one of these monomers (1) to (5) with monomers other than these monomers are more preferable.
  • the structural unit derived from any one of the above monomers (1) to (5) is contained in an amount 10 mol% or more, preferably 20 mol% or more and still more preferably 25 mol% or more of such a copolymer.
  • Examples of the monomer used in combination with any one of the monomers (1) to (5) include the following compounds (6) to (16).
  • Acrylates and methacrylates having an aliphatic hydroxyl group for example, 2-hydroxyethylacrylate or 2-hydroxyethylmethacrylate.
  • (Substituted) alkylacrylates such as methylacrylate, ethylacrylate, propylacrylate, butylacrylate, amylacrylate, hexylacrylate, octylacrylate, benzylacrylate, 2-chloroethylacrylate, glycidylacrylate and N-dimethylaminoethylacrylate.
  • alkylmethacrylates such as methylmethacrylate, ethylmethacrylate, propylmethacrylate, butylmethacrylate, amylmethacrylate, hexylmethacryl ate, cyclohexylmethacrylate, benzylmethacrylate, glycidylmethacrylate and N-dimethylaminoethylmethacrylate.
  • (9) Acrylamide or methacrylic acid amides such as acrylamide, methacrylamide, N-methylolacrylamide, N-ethylacrylamide, N-hexylmethacrylamide, N-cyclohexylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-nitrophenylacrylamide and N-ethyl-N-phenylacrylamide.
  • 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.
  • Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate.
  • Styrenes such as styrene, ⁇ -methylstyrene, methylstyrene and chloromethyl styrene.
  • 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.
  • N-vinylpyrrolidone N-vinylcarbazole, 4-vinylpyridine, acrylonitrile and methacrylonitrile.
  • Unsaturated imides such as maleimide, N-acryloylacrylamide, N-acetylmethacrylamide, N-propionylmethacrylamide and N-(p-chlorobenzoyl)methacrylamide.
  • the polymer compound preferably has a weight average molecular weight of 2,000 or more and a number average molecular weight of 1000 or more, and more preferably has a weight average molecular weight of 5,000 to 300,000, a number average molecular weight of 2,000 to 250,000 and a degree of dispersion (the weight average molecular weight/the number average molecular weight) of 1.1 to 10.
  • water-insoluble and aqueous alkali solution-soluble urethane polymer compound examples include, though not limited to, urethane type polymer compounds described in each publication of JP-A Nos. 63-124047 , 63-287946 , 2-866 and 2-156241 .
  • the acryl polymer compound may be used together with the urethane polymer compound.
  • alkali-soluble novolac resin used in the invention may include alkali-soluble novolac resins such as a phenolformaldehyde resin, m-cresolformaldehyde resin, p-cresolformaldehyde resin, m-/p- mixed cresolformaldehyde resin and phenol/cresol (any of m-, p- and m-/p- mixture) mixed formaldehyde resin.
  • alkali-soluble novolac resins those having a weight average molecular weight of 500 to 20,000 and a number average molecular weight of 200 to 10,000 are used.
  • a condensate of a phenol having an alkyl group having 3 to 8 carbon atoms as a substituent and formaldehyde such as a t-butylphenolformaldehyde resin and octylphenolformaldehyde resin as described in U.S. Patent No. 4,123,279 may be used together.
  • the alkali-soluble novolak resin preferably has a high content of a novolak resin, the bonding property of an ortho position thereof being high.
  • the novolak resin include a xylenol cresol formaldehyde resin, a m-cresol formaldehyde resin or a p-cresol formaldehyde resin. Any of those specific novolak resins are preferably contained in an amount of preferably 10% by mass or more, and more preferably 30% by mass or more relative to the total amount of the whole novolak resin used in the alkali-soluble novolak resin.
  • the lower recording layer having a resin matrix phase containing the thus formed dispersion phase contains, in the dispersion phase, a compound which changes solubility to an alkaline solution by an infrared absorber and heat in a high content in the case that the lower recording layer is a positive recording layer, thereby efficiently improves solubility of the polymer matrix phase to an alkaline solution.
  • the resin included in the dispersion phase in microcapsule form in the invention can be easily prepared by methods described in the examples of JP-A No. 1-145190 or the method described in " NEW EDITION, MICROCAPSULE-ITS PREPARATION, NATURE AND APPLICATION” published by Sankyo Shuppan .
  • the resin included in the dispersion phase in latex form in the invention can be produced by methods shown in JP-A Nos. 10-265710 , 10-270233 or 5-2281 or " CHEMISTRY OF POLYMER LATEX” issued from Polymer Publishing Association and " POLYMER LATEX” published by New Polymer Library .
  • Examples of materials which can be included in the microcapsule or in the latex include an acid generator, an initiator such as a radical generator, a light-heat converting material and a crosslinking agent.
  • Examples of the polymer compound which can be used for the polymer matrix phase for forming the lower recording layer having the dispersion phase of an embodiment (2) include the compounds exemplified for the dispersion phase of an embodiment (1).
  • the dispersion phase may contain an acid generator that is decomposed by light or heat to generate an acid, to improve the solubility of the aqueous alkali-soluble polymer compound of an exposed portion in aqueous alkali.
  • the "acid generator” means those that are decomposed by irradiation with light having a wavelength of 200 nm to 500 nm or by heating at 100°C or more.
  • the acid generator examples include a photoinitiator for photo-cationic polymerization, photoinitiator for photo-radical polymerization, photo-achromatizing agent for dyes, photo-discoloring agent, known acid generator used for micro-resist, known compound which is thermally decomposed to generate an acid and a mixture of these compounds.
  • the acid which is generated from the acid generator is preferably a strong acid having a pKa of 2 or less such as sulfonic acid and hydrochloric acid.
  • the initiator include the triazine compounds described in JP-A No. 11-95415 and the latent Bronsted acid described in JP-A No. 7-20629 .
  • the latent Bronsted acid means a precursor that is to be decomposed to generate a Bronsted acid. It is assumed that the Bronsted acid catalyzes a matrix generating reaction between a resol resin and a novolac resin.
  • Typical examples of the Bronsted acid fitted to this purpose include trifluoromethanesulfonic acid and hexafluorophosphonic acid.
  • An ionic latent Bronsted acid may be preferably used in the invention.
  • the ionic latent Bronsted acid include onium salts, particularly, iodonium, sulfonium, phosphonium, selenonium, diazonium and arsonium salts.
  • Particularly useful and specific examples of the onium salt include diphenyliodonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, phenylmethyl-ortho-cyanobenzylsulfoniumtrifluoromethane sulfonate and 2-methoxy-4-aminophenyldiazonium hexafluorophosphate.
  • Nonionic latent Bronsted acids are also appropriately used in the invention.
  • these nonionic latent Bronsted acids include compounds represented by the following formula: RCH 2 X, RCHX 2 , RCX 3 , R(CH 2 X) 2 and R(CH 2 X) 3 (wherein X represents Cl, Br, F or CF 3 SO 3 and R represents an aromatic group, an aliphatic group or a combination of an aromatic group and an aliphatic group).
  • Useful ionic latent Bronsted acid is those represented by the following formula.
  • R 3 and R 4 respectively represent a lone electron pair and R 1 and R 2 respectively represent an aryl or substituted aryl group when X is iodine.
  • R 4 represents a lone electron pair and R 1 , R 2 and R 3 respectively represent an aryl group, a substituted aryl group, an aliphatic group or substituted aliphatic group.
  • R 4 represents an aryl group, a substituted aryl group, an aliphatic group or a substituted aliphatic group.
  • W represents BF 4 , CF 3 SO 3 , SbF 6 , CCl 3 CO 2 , ClO 4 AsF 6 , PF 6 or may be any corresponding acid having a pH less than 3.
  • All the onium salts described in U.S. patent No. 4,708,925 may be used as the latent Bronsted acid used in the invention. Examples of these onium salts include indonium, sulfonium, phosphonium, bromonium, chloronium, oxysulfoxonium, oxysulfonium, sulfoxonium, selenonium, telluronium and arsonium.
  • diazonium salt as the latent Bronsted acid.
  • These diazonium salts provide a sensitivity equivalent to that of other latent Bronsted acids in the infrared region and a higher sensitivity than other latent Bronsted acid in the ultraviolet region.
  • the acid generator can be added in a proportion of 0.01 to 50% by mass, preferably 0.1 to 25% by mass and more preferably 0.5 to 20% by mass with respect to the total solid content of the lower recording layer from the viewpoint of image forming characteristics and from the viewpoint of preventing a non-image portion from being contaminated.
  • the positive recording layer in the invention contains an infrared absorbing agent that is a structural component which develops a light-to-heat converting function.
  • This infrared absorbing agent has the ability to convert absorbed infrared rays into heat.
  • Laser scanning causes the infrared absorbing agent to lose the interaction, a developing inhibitor to decompose and generates an acid, which significantly improves the solubility of the infrared absorbing agent.
  • the infrared absorbing agent itself interacts with the alkali-soluble resin to suppress alkali-solubility.
  • the infrared absorbing agent used in the invention is dyes or pigments which efficiently absorb infrared rays having a wavelength from 760 nm to 1,200 nm and is preferably dyes or pigments having an absorption maximum in a wavelength range from 760 nm to 1,200 nm.
  • the infrared absorbing agent which can be used preferably for the planographic printing plate precursor of the invention will be hereinafter explained in detail.
  • the dyes may be commercially available ones and known ones described in publications such as " Dye Handbook" (edited by the Society of Synthesis Organic Chemistry, Japan, and published in 1970 ). Specific examples thereof include azo dyes, metal complex azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, cyanine dyes, squarylium dyes, pyrylium dyes, metal thiolate complexes, and the like.
  • the dye include cyanine dyes described in JP-A Nos. 58-125246 , 59-84356 , 59-202829 , and 60-78787 ; methine dyes described in JP-A Nos. 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 ; squarylium 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.
  • JP-B Japanese Patent Application Publication
  • the dye further include near infrared absorbing dyes represented by formulae (I) or (II) described in U.S. Patent No. 4,756,993 .
  • these dyes particularly preferable are cyanine dyes, squarylium dyes, pyrylium salts, and nickel thiolate complexes.
  • the pigment which can be 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.
  • These pigments may be used with or without surface treatment.
  • a method of the 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
  • the particle size of the pigment is preferably from 0.01 ⁇ m to 10 ⁇ m, more preferably from 0.05 ⁇ m to 1 ⁇ m, and even more preferably from 0.1 ⁇ m to 1 ⁇ m.
  • any known methods for dispersing technique used to produce ink or toner can be used for dispersing the pigment in the invention.
  • a machine which can be used for the dispersing 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 planographic printing plate precursor of the invention has a positive recording layer.
  • the positive recording layer utilizes a positive action, in which solubility of an unexposed portion in an alkali developer is suppressed while the suppression of the solubility is cancelled in an exposed portion.
  • an infrared absorbing agent which causes the cancellation by interacting with a binder polymer having a specific functional group.
  • the infrared absorbing agent has an onium salt structure.
  • cyanine dyes and pyrylium salts are particularly preferable. The details of these cyanine dyes and pyrylium salts are as described above.
  • an anionic infrared absorbing agent as described in JP-A No. 11-338131 is also preferably used.
  • This anionic infrared absorbing agent represents those having no cationic structure but an anionic structure on the mother nucleus of a dye which substantially absorbs infrared rays.
  • the anionic infrared absorbing agent include (a-1) an anionic metal complex and (a-2) an anionic phthalocyanine.
  • the anionic metal complex (a-1) denotes a compound in which the core metal and the ligands in the complex part that substantially absorbs light are an anion as a whole.
  • the anionic phthalocyanine (a-2) denotes a compound in which an anionic group such as a sulfonic acid, carboxylic acid or phosphonic acid group is bonded as a substituent with a phthalocyanine skeleton to form an anion as a whole.
  • the anionic phthalocyanine further include anionic infrared absorbing agents represented by the formula [Ga - -M-Gb] m X m+ (Ga represents an anionic substituent, Gb - represents a neutral substituent, and X m+ represents a cation having a valency of 1 to m (where m denotes an integer from 1 to 6) including a proton) as described in JP-A No. 11-338131 .
  • the infrared absorbing agent used in the positive recording layer is preferably a dye.
  • the dye include that having an onium salt structure as described in JP-A No. 11-291652 , paragraphs [0018] to [0034].
  • infrared absorbing agent such as the cyanine dye, pyrylium salt dye or anionic dye, which exhibit dissolution inhibitive ability
  • other dyes or pigments may be used together in the recording layer of the planographic printing plate precursor of the invention in view of further improving sensitivity and developing latitude.
  • the infrared absorbing agent is preferably added in an amount of 0.01% to 50% by mass, more preferably 0.1% to 20% by mass and more preferably 0.5% to 15% by mass based on the total solid content in each of the lower recording layer and other layers from the viewpoint of image formation characteristics and from the viewpoint of suppressing generation of contamination to a non-image portion.
  • the infrared absorbing agent may be contained in either or both of the matrix phase and the dispersion phase.
  • the infrared absorbing agent may be added together with the raw materials when the latex particles are formed or may be introduced after the latex is formed.
  • Examples of the method of introducing the infrared absorbing agent into the latex after the latex is formed include a method in which a water system, in which desired components such as the initiator, a coloring material or a crosslinking agent to be introduced in the latex are dissolved in an organic solvent, is added to the dispersion medium.
  • the recording layer of the planographic printing plate precursor of the invention is resistant to abrasion in relation to an infrared laser irradiation system.
  • any polymer material may be used as a binder which forms the recording layer as long as its solubility to an aqueous alkali, namely, an alkali developing solution, is changed by imparting thermal energy
  • the ceiling temperature of the polymer is given as an example of an index of the abrasion resistance.
  • This ceiling temperature is a temperature at which the rate of a polymerization reaction is equal to the rate of a depolymerization reaction. It is preferable to select polymers having a high ceiling temperature to obtain high abrasion resistance.
  • a proper polymer may be selected using the decomposition temperature thereof as an index.
  • the polymer that is a component of the recording layer may be a polymer having a decomposition temperature of preferably 150°C or more and more preferably 200°C or more. When the decomposition temperature is less than 150°C, this may not be preferable because the possibility of abrasion can be increased.
  • Each component other than the polymer compound contained in the recording layer preferably has a decomposition temperature of 150°C or more, while a small amount of a component having a decomposition temperature less than 150°C may also be contained as long as it gives substantially no problem.
  • the lower recording layer should have a configuration to achieve the dispersion phase.
  • Additives which can be used in the other recording layers may basically be used in the lower recording layer as long as the requirement of the lower recording layer is satisfied.
  • Each recording layer of the invention is preferably compounded of a fluorine-containing polymer for the purpose of improving the resistance to development in an image region.
  • fluorine-containing polymer used in an image recording layer include copolymers formed from fluorine-containing monomers as described in each of JP-ANos. 11-288093 and 2000-187318 .
  • fluorine-containing polymer examples include fluorine-containing acryl polymers P-1 to P-13 as described in JP-A No. 11-288093 and fluorine-containing polymers obtained by copolymerizing fluorine-containing acryl monomers A-1 to A-33 with arbitrary acryl monomers.
  • the fluorine-containing polymer exemplified above preferably has a weight average molecular weight of 2,000 or more and a number average molecular weight of 1,000 or more. It is more preferable that the weight average molecular weight is 5,000 to 300,000 and the number average molecular weight is 2,000 to 250,000.
  • fluorine surfactants having the preferable molecular weight may be used as the fluorine-containing polymer.
  • specific examples of such surfactants include MEGAFACE F-171, F-173, F-176, F-183, F-184, F-780 and F-781 (all are trade names, manufactured by DIC Corporation).
  • fluorine-containing polymers may be used either singly or combinations of two or more. It is necessary that the amount of the fluorine-containing polymer is 1.4 mass% or more based on the solid content of the image recording layer to meet the requirements in the invention. The amount is preferably 1.4 to 5.0 mass%. When the amount is below 1.4 mass%, the purpose of the addition of the fluorine-containing polymer, namely, the effect of improving the developing latitude of the image recording layer may become insufficient.
  • a dissolution inhibitor which is a thermally decomposable material and substantially reduces the solubility of the aqueous alkali-soluble polymer compound in an decomposed state, may be additionally used in the lower recording layer or other layers of the precursor of the invention according to the need.
  • the dissolution inhibitor include an onium salt, an o-quinonediazide compound, an aromatic sulfone ester compound and an aromatic sulfonate compound.
  • the addition of the dissolution inhibitor makes it possible not only to improve the dissolution resistance of the image portion in a developing solution but also to use, as the infrared absorbing agent, a compound which does not interact with the alkali-soluble resin.
  • the onium salt include diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts and arsonium salts.
  • 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-A No. 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.
  • a diazonium salt is particularly preferably used as the dissolution inhibitor.
  • Particularly preferable examples of the diazonium salt include those described in JP-A No. 5-158230 .
  • 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-benz
  • hexafluorophosphoric acid, and alkylaromatic sulfonic acids such as triisopropylnaphthalenesulfonic acid and 2,5-dimethylbezenesulfonic acid are particularly preferable.
  • the quinonediazide include 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 solubilization property of the photosensitive material from the effects of losing the function of suppressing the dissolution of the binder by being thermally decomposed as well as the effect that the o-quinonediazide itself is changed into an alkali-soluble material.
  • Preferable examples of the o-quinonediazide compound used in the invention include compounds described in J.
  • sulfonic acid esters or sulfonamides of o-quinonediazide made to react with various aromatic polyhydroxy compounds or with aromatic amino compounds.
  • o-quinonediazide compound further include an ester 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.
  • o-quinonediazide compound further 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.
  • Other useful o-quinonediazide compounds are reported in unexamined or examined patent documents, examples of which include JP-A Nos. 47-5303 , 48-63802 , 48-63803 , 48-96575 , 49-38701 and 48-13354 , JP-B No.
  • the amount of the o-quinonediazide compound is preferably in a range from 1 mass% to 50 mass%, more preferably in a range from 5 mass% to 30 mass%, and particularly preferably in a range from 10 mass% to 30 mass% based on the total solid content of each recording layer. These compounds may be used singly or as a mixture of plural kinds thereof.
  • the amount of the additives except for the o-quinonediazide compound is preferably 1 mass% to 50 mass%, more preferably 5 mass% to 30 mass%, and particularly preferably 10 mass% to 30 mass%.
  • the additives and binder used in the invention are preferably compounded in the same layer.
  • a polymer having, as a polymerization component, a (meth)acrylate monomer having two or three perfluoroalkyl group having 3 to 20 carbon atoms in its molecule as described in the specification of JP-A No. 2000-87318 may be used together for the purpose of intensifying the discrimination of an image to be formed and increasing resistance to surface damages of the precursor of the invention.
  • the recording layer may further contain a cyclic acid anhydride, a phenolic compound, an organic acid or the like.
  • a 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 content thereof 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 in terms to the total solid content of the recording layer.
  • a dye having an absorption in the visible light region may be added to each recording layer according to the invention as a colorant for an image to be formed.
  • the dye include 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 (these products are manufactured by Orient Chemical Industries, Ltd.), Victoria Pure Blue, Crystal Violet (CI42555), Methyl Violet (CI42535), Ethyl Violet, Rhodamine B (CI145170B), Malachite Green (CI42000), Methylene Blue (CI52015), AIZEN SPIROL BLUE C-RH (manufactured by Hodogaya Chemical Co., Ltd.), and dyes as described in JP-A No. 62-293247 .
  • the addition of these dyes is preferable because discrimination between an image portion and a non-image portion can be intensified after an image is formed.
  • the amount of these dyes to be added is preferably in a range from 0.01 to 10 mass % based on the total solid content of the recording layer.
  • 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 , and/or copolymers made from a fluorine-containing monomer as described in JP-ANo. 11-288093 can be added to the image recording layer of the planographic printing plate precursor of the invention in order to make processes more stable upon development conditions in processes.
  • 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: "AMOGEN 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 such as DBE-224, DBE-621, DBE-712, DBE-732, and DBE-534 (all trade names:, manufactured by Chisso Corporation) or TEGO ® GLIDE 100 (trade name, manufactured by Tego Chemie, Essen, Germany).
  • the content of the nonionic surfactant and/or the amphoteric surfactant is preferably from 0.05% to 15% by mass, and more preferably from 0.1% to 5% by mass with respect to the total solid content of the photosensitive composition.
  • a printing-out agent which is a material 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, may be added to the photosensitive composition of the invention.
  • a typical example of the printing-out agent is a combination of a photo acid-generating agent (a compound which is heated by exposure to light, thereby generating an acid), and an organic dye which can form salts.
  • the combination 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 stability over the passage of time and produce a clear printed-out image.
  • Examples of the photo-acid releasing agent further include various o-naphthoquinonediazide compounds as described in JP-A No. 55-62444 ; 2-trihalomethyl-5-aryl-1,3,4-oxadiazole compound as described in JP-A No. 55-77742 ; and diazonium salts.
  • a plasticizer may be added to a coating liquid for forming the recording layer of the precursor of the invention to give flexibility to a coating film made from the coating liquid.
  • 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/or methacrylic acid.
  • planographic printing plate precursor of the invention may be usually produced by sequentially applying, to an appropriate support, coating liquids for forming respective recording layers which contain the components.
  • Examples of a solvent appropriate for applying the recording layer include, though not limited to, ethylene dichloride, cyclohexanone, methyl ethyl ketone, methanol, ethanol, propanol, ethylene glycol monomethyl ether, 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, ⁇ -butyrolactone and toluene. These solvents may be used either singly or as a mixture of two or more of them.
  • the concentration of the above components (total solid content including additives) in the solvent is preferably 1 mass% to 50 mass%.
  • the lower recording layer and upper recording layers are preferably formed so as to form two layers separate from each other in principle.
  • Examples of the method of forming the separate two layers include, though not limited to: a method utilizing a difference between the solubility of the components contained in the lower recording layer to a solvent and that of the components contained in the upper layer; and a method in which a solvent is vaporized and removed quickly by drying after the upper layer is applied.
  • Examples of the method utilizing the difference between the solubility of the components contained in the lower recording layer to a solvent and that of the components contained in the upper layer include a method which uses a solvent which does not dissolve the alkali-soluble resin contained in the lower recording layer when an upper layer coating liquid is applied. This makes it possible to separate each layer clearly to form coating films even if two-layer coating is carried out.
  • components insoluble in solvents such as methyl ethyl ketone and 1-methoxy-2-propanol which dissolve the alkali-soluble resin which is the upper layer component, are selected as the lower recording layer components; the lower recording layer is applied by using a solvent which contain the lower recording layer components dissolved therein and dried; the upper layer components, which have the alkali-soluble resins as a primary component, are dissolved in methyl ethyl ketone, 1-methoxy-2-propanol or the like; and the upper layer coating liquid is applied and dried, whereby the formation of two layers can be attained.
  • solvents such as methyl ethyl ketone and 1-methoxy-2-propanol
  • a solvent which dissolves the alkali-soluble resin contained in the lower recording layer may be mixed with a solvent which doe not dissolve this alkali-soluble resin.
  • Mixing of components which causes between the upper layer and the lower recording layer can be arbitrarily controlled by changing the mixing ratio of both solvents. If the ratio of the solvent that dissolves the alkali-soluble resin contained in the lower recording layer is increased, a part of the lower recording layer is dissolved when applying the upper layer and the dissolved component becomes to be contained in the upper layer as a particle-shape component after the upper layer is dried.
  • the particle-shape component forms projections provided on the surface of the upper layer, which increases damage resistance.
  • the dissolution of the lower recording layer components tends to deteriorate the quality of the lower recording layer and hence tends to deteriorate resistance of the lower recording layer against chemicals.
  • controlling of the mixing ratio with taking the characteristics of each solvent into account enables exhibition of various characteristics as well as making layers being partially compatible therebetween, which is explained below.
  • the amount of a solvent which can dissolve the alkali-soluble resin in the lower recording layer is preferably 80 mass% or less relative to the amount of the solvent used to the upper layer coating liquid from the viewpoint of resistance to chemicals, and taking resistance to damage into account, it is more preferably in a range from 10 mass% to 60 mass%.
  • Examples of a method of drying a solvent very quickly after the second layer (upper recording layer) is applied include a method including spraying high pressure air from a slit nozzle located at almost a right angle with respect to the running direction of a web, a method including supplying, to a web, thermal energy as conductive heat from the underside of the web through a roll (heating roll) to which a heating medium such as steam is supplied, and a combination of these methods.
  • Various methods may be used as a method of applying each of the layers such as the image recording layer.
  • Examples of the coating method may include bar coater coating, rotation coating, spray coating, curtain coating, dip coating, air knife coating, blade coating and roll coating.
  • the coating method used to form the upper recording layer is preferably carried out in a non-contact system to prevent damages to the lower recording layer when applying the upper recording layer. While bar coater coating, though it is a contact system, may be used as the method generally used in a solvent system coating, it is desirable to carry out the coating in forward driving to prevent damages to the lower recording layer.
  • the coating amount of the lower recording layer after the layer is dried in the planographic printing plate precursor of the invention is preferably in a range from 0.5 g/m 2 to 1.5 g/m 2 and more preferably in a range from 0.7 g/m 2 to 1.0 g/m 2 from the viewpoint of suppressing generation of a residual film during developing of the precursor and ensuring printing durability of a printing plate formed from the precursor.
  • the amount of other recording layer (upper recording layer) after drying is preferably in the range of 0.05 g/m 2 to 1.0 g/m 2 , more preferably in the range of 0.07 g/m 2 to 0.7 g/m 2 .
  • a surfactant such as a fluorine surfactant as described in JP-A No. 62-170950 may be added to the coating liquid for the lower recording layer or the coating liquids of other recording layers to improve coating characteristics.
  • the amount of the surfactant is preferably 0.01 mass% to 1 mass% and more preferably 0.05 mass% to 0.5 mass% based on the total solid content of the coating liquid.
  • the support used in the planographic printing plate precursor of the invention is a plate-shape material having dimensional stability.
  • examples thereof include paper, papers laminated with plastic (such as polyethylene, polypropylene or polystyrene), metal plates (such as aluminum plates, zinc plates or copper plates), plastic films (such as cellulose biacetate films, cellulose triacetate films, cellulose propionate films, cellulose lactate films, cellulose acetate lactate films, cellulose nitrate films, polyethylene terephthalate films, polyethylene films, polystyrene films, polypropylene films, polycarbonate films, or polyvinyl acetate films), and papers or plastic films on which a metal such as aluminum, zinc or copper is laminated or vapor-deposited.
  • plastic such as polyethylene, polypropylene or polystyrene
  • metal plates such as aluminum plates, zinc plates or copper plates
  • plastic films such as cellulose biacetate films, cellulose triacetate films, cellulose propionate films, cellulose lactate films,
  • the support is preferably a polyester film or an aluminum plate, and more preferably an aluminum plate, since an aluminum plate is excellent in terms of dimensional stability and is also relatively inexpensive.
  • Preferable examples of 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.
  • other elements which may be 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 mm to 0.6 mm, preferably from 0.15 mm to 0.4 mm, and more preferably from 0.2 mm to 0.3 mm.
  • the aluminum plate may be arbitrarily subjected to degreasing treatment prior to the surface-roughening 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, or 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 arbitrarily 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°C to 70°C, a current density of 5 A/dm 2 to 60 A/dm 2 , a voltage of 1 V 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 durability 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.
  • Example of the hydrophilization treatment include a method using an alkali metal silicate (for example, an aqueous sodium silicate solution) 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 of the invention has at least two layers including the lower recording layer and other layer(s) (upper recording layer(s)) which are provided on the support, the planographic printing plate precursor may further has an undercoat layer provided between the support and the lower recording layer according to the need.
  • organic compounds can be used as components of the undercoat layer.
  • examples thereof include carboxymethylcellulose, dextrin, gum arabic, phosphonic acids having an amino group, such as 2-aminoethylphosphonic acid, organic phosphonic acids which may have a substituent, such as phenyl phosphonic acid, naphthylphosphonic acid, alkylphosphonic acid, glycerophosphonic acid, methylenediphosphonic acid and ethylenediphosphonic acid, organic phosphoric acids which may have a substituent, such as phenylphosphoric acid, naphthylphosphoric acid, alkylphosphoric acid and glycerophosphoric acid, organic phosphinic acids which may have a substituent, such as phenylphosphinic acid, naphthylphosphinic acid, alkylphosphinic acid and glycerophosphinic acid, amino acids such as glycine and ⁇ -alanine, and hydrochlorides of amines having a
  • Examples of the method for forming the organic undercoat layer include: a method including applying, onto the aluminum plate, a solution in which the above-mentioned organic compound is dissolved in water, or an organic solvent such as methanol, ethanol or methyl ethyl ketone, or a mixed solvent thereof and then drying the resultant aluminum plate; and a method including immersing the aluminum plate into a solution in which the above-mentioned organic compound is dissolved in water or an organic solvent such as methanol, ethanol, methyl ethyl ketone or a mixed solvent thereof so as to adsorb the compound, washing the aluminum plate with water or the like, and then drying the resultant aluminum plate.
  • the solution of the organic compound having a concentration of 0.05 to 10% by mass may be applied in various ways.
  • the concentration of the organic compound in the solution is from 0.01 to 20%, preferably from 0.05 to 5%
  • the temperature for the immersion is from 20 to 90°C, preferably from 25 to 50°C
  • the time taken for immersion is from 0.1 second to 20 minutes, preferably from 2 seconds to 1 minute.
  • the pH of the solution used in the above-mentioned methods can be adjusted into a range of 1 to 12 with a basic material such as ammonia, triethylamine or potassium hydroxide, or an acidic material such as hydrochloric acid or phosphoric acid.
  • a yellow dye may be added to the solution, in order to improve the tone reproducibility of the recording layer.
  • the amount of the organic undercoat layer applied is suitably from 2 mg/m 2 to 200 mg/m 2 , and is preferably from 5 mg/m 2 to 100 mg/m 2 .
  • the positive planographic printing plate precursor produced as described above is usually subjected to image exposure and developing treatment.
  • the planographic printing plate precursor is exposed to light from a light source which preferably has an emitting wavelength in the near-infrared region to the infrared region.
  • the planographic printing plate precursor is preferably exposed imagewise to light from a solid laser or a semiconductor laser radiating infrared rays having a wavelength of 760 nm to 1,200 nm.
  • the planographic printing plate precursor of the invention is developed using water or an alkali developing solution after exposure.
  • heating treatment may be carried out between an exposure step and a developing step.
  • the heating is preferably carried out at a temperature range from 60°C to 150°C for 5 seconds to 5 minutes.
  • the heating method conventionally known various methods may be used. Examples of the heating method include a method in which a recording material is heated with bringing it into contact with a panel heater or ceramic heater and a non-contact method using a lamp or hot air. This heat treatment enables to reduce the energy required for recording when a laser is applied.
  • Any conventionally known aqueous alkali solution may be used as a developing solution and replenishing solution to be used for plate-making of the planographic printing plate of the invention.
  • the developing solution which may be applied to the developing treatment of the planographic printing plate precursor of the invention is a developing solution having a pH range from 9.0 to 14.0 and preferably a pH range from 12.0 to 13.5.
  • a conventionally known aqueous alkali solution may be used as the developing solution (hereinafter referred to as a developing solution including a replenishing solution).
  • alkali agent for the aqueous alkali solution 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 or lithium hydroxide; and organic alkali agents such as monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, ethylene
  • an aqueous alkali solution having a non-reducing sugar and a base may also be used.
  • the non-reducing sugar denotes a sugar having no reducing ability due to lack of a free aldehyde group, a ketone group and the like, and is classified into trehalose oligosaccharides in which reducing groups are combined with other, glycosides in which reducing groups of sugars are combined with non-sugars, or sugar alcohols in which sugars are reduced by hydrogenation. Any of these non-reducing sugars may be preferably used.
  • Examples of the trehalose 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) are preferable.
  • 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 combination of two or more thereof.
  • the content of the nonreducing sugar in the developer is preferably from 0.1% to 30% by mass, more preferably from 1%to 20% by mass with respect to the total amount of the developer.
  • the base combined with the nonreducing sugar(s) may be an alkali agent that has been conventionally known.
  • 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 or ammonium borate; and organic alkali agents such as monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, ethyleneimine, ethylenediamine, or pyridine.
  • inorganic alkali agents such as sodium hydroxide,
  • the alkali agent may be used singly or in combination of two or more.
  • the alkali agents sodium hydroxide and potassium hydroxide are preferable.
  • the reason is that pH adjustment can be made in a wide pH range by regulating the amount of the alkali agent to be added to the non-reducing sugar.
  • trisodium phosphate, sodium carbonate, potassium carbonate or the like itself have a buffer action and are hence preferable.
  • an aqueous solution having a higher alkali intensity than that of the developer can be added to the developer. It is known that this enables to treat a great number of photosensitive plates without recourse to replacing the developer in the developing tank over a long period of time.
  • This replenishing manner is also preferably used in the invention.
  • various surfactants or organic solvents can be incorporated into the developer and the replenisher in order to promote and suppress development capacity, disperse scum generated during development, and enhance the ink-affinity of image portions of the printing plate.
  • the surfactant include anionic surfactants, cationic surfactants, nonionic surfactants and amphoteric surfactants.
  • a reducing agent such as hydroquinone, resorcin, a sodium or potassium salt of an inorganic acid such as sulfurous acid or hydrogen sulfite acid
  • an organic carboxylic acid such as sulfurous acid or hydrogen sulfite acid
  • an antifoaming agent such as sodium or potassium salt of an inorganic acid such as sulfurous acid or hydrogen sulfite acid
  • a water softener such as sodium or potassium salt of an inorganic acid such as sulfurous acid or hydrogen sulfite acid
  • the printing plate developed with the developer and replenisher described above is subsequently subjected to treatments with washing water, a rinse solution containing a surfactant and other components, and a desensitizing solution containing gum arabic and a starch derivative.
  • Various combinations of these treatments may be employed for after treatment when the photosensitive composition precursor of the invention is to be used for forming a planographic printing plate.
  • automatic developing machines for printing plate precursors have been widely used in order to rationalize and standardize plate-making processes in the plate-making and printing industries.
  • These automatic developing machines are generally made up of a developing section and a post-processing section, and include a device for carrying printing plate precursors, various treating solution tanks, and spray devices.
  • These machines are machines for spraying respective treating solutions, which are pumped up, onto an exposed printing plate through spray nozzles, for development, while the printing plate is transported horizontally.
  • a method has also attracted attention in which a printing plate precursor is immersed in treating solution tanks filled with treating solutions and conveyed by means of in-liquid guide rolls.
  • Such automatic processing can be performed while replenishers are being replenished into the respective treating solutions in accordance with the amounts to be treated, operating times, and other factors.
  • a so-called use-and-dispose processing manner can also be used, in which treatments are conducted with treating solutions which in practice have yet been used.
  • a method of treating the heat-sensitive planographic printing plate precursor of the invention will be explained.
  • unnecessary image portions for example, a film edge mark of an original picture film
  • unnecessary image portions can be erased.
  • the erasing is preferably performed by applying an erasing solution to unnecessary image portions, leaving the printing plate as it is for a given time, and washing the plate with water, as described in, for example, JP-B No. 2-13293 .
  • This erasing may also be performed by a method of radiating active rays introduced through an optical fiber onto the unnecessary image portions, and then developing the plate, as described in JP-A No. 59-174842 .
  • planographic printing plate obtained as described above is, if desired, coated with a desensitizing gum, and subsequently the plate can be made available for printing.
  • burning treatment can be applied to the planographic printing plate.
  • the planographic printing plate is subjected to the burning treatment, it is preferable that the plate is treated with a surface-adjusting solution before the burning treatment takes place as described in JP-B No. 61-2518 , or JP-A Nos. 55-28062 , 62-31859 or 61-159655 .
  • Examples of the method of the surface-adjusting treatment include: a method of applying the surface-adjusting solution onto the planographic printing plate with a sponge or absorbent cotton infiltrated with the solution; a method of immersing the planographic printing plate in a vat filled with the surface-adjusting solution; and a method of applying the surface-adjusting solution to the planographic printing plate with an automatic coater.
  • a method of applying the surface-adjusting solution onto the planographic printing plate with a sponge or absorbent cotton infiltrated with the solution a method of immersing the planographic printing plate in a vat filled with the surface-adjusting solution
  • a method of applying the surface-adjusting solution to the planographic printing plate with an automatic coater When the amount of solution applied is made uniform with a squeegee or a squeegee roller after application, a better result may be obtained.
  • the amount of surface-adjusting solution applied is suitably from 0.03 g/m 2 to 0.8 g/m 2 (dry mass).
  • the planographic printing plate onto which the surface-adjusting solution is applied can be dried, and then the plate is heated to a high temperature by means of a burning processor (for example, a burning processor BP-1300 (trade name, available from FUJIFILM Corporation)) or the like.
  • the heating temperature and the heating time which depend on the kind of components forming the image, are preferably from 180°C to 300°C and from 1 minute to 20 minutes, respectively.
  • a planographic printing plate subjected to burning treatment can be further subjected to treatments which have been conventionally conducted, such as a water-washing treatment and gum coating.
  • the so-called desensitizing treatment for example, gum coating
  • the planographic printing plate obtained as a result of such treatments can be applied to an offset printing machine or to some other printing machine, and can be used for printing on a great number of sheets.
  • Exemplified Monomers (1), (2), (8), (9) and (13) used for forming the specific polymers according to the invention can be synthesized using the methods described in Hofmann et al., Markromoleculare Cheme, vol. 177, pp. 1791-1813 (1976 ), and persons skilled in the art can easily obtain similar monomers through selection of some different starting materials.
  • Exemplified Monomer (11) can be synthesized using a method similar to the method described in Kang and Bae, Journal of Controlled Release, vol. 80, pp. 145-155 . Details of the synthesis method are as follows. 4-Amino-N-(6-methoxy-3-pyridazinyl)-benzosulfonamide in an amount of 10 g (35.6 mmol) was dispersed and dissolved in 120 ml of acetonitrile, and thereto was added a solution prepared by dissolving 1.42 g (35.6 mmol) of sodium hydroxide in 30 ml of water.
  • the reactant solution thus prepared was cooled to -10°C, and the reaction with methacryloyl chloride was allowed to continue for 1 hour in a reaction vessel at ordinary temperatures.
  • 10 mg of BHT was added to the reaction solution obtained.
  • the resulting mixture was dried under normal atmospheric pressure.
  • the oily residue thus obtained was dissolved in a mixture of 150 ml of methylene chloride and 100 ml of 2N HCl.
  • a reaction product was separated by using 50 ml of methylene chloride, 520 ml of 2N HCl and 100 ml of water, dried over MgSO 4 and then refluxed under normal atmospheric pressure.
  • the thus obtained synthesis product was purified by column chromatography. Thus, 2.39 g of Exemplified monomer (11) was obtained (in a 19% yield).
  • Exemplified Monomer (4) can be synthesized by a method similar to the method by which Exemplified Monomer (11) is synthesized, except that acryloyl chloride is used in place of methacryloyl chloride.
  • 4-Amino-N-(2,6-dimethyl-4-pyrimidinyl)-benzosulfonamide in an amount of 24.9 g (89.5 mmol) was dispersed and dissolved in 500 ml of acetonitrile, and thereto was added a solution prepared by dissolving 8.10 g (89.5 mmol) of potassium hydroxide in 75 ml of water.
  • the reactant solution thus prepared was cooled to 0°C, and the reaction with acryloyl chloride was allowed to continue for 14 hours in a reaction vessel at ordinary temperatures. A small amount of precipitate formed was filtered off.
  • the resulting reaction solution was mixed with 25 mg of BHT, and dried under normal atmospheric pressure. The residue thus obtained was dissolved in 350 ml ofrefluxing methanol. After cooling to room temperature, the methanol solution was added to 1.6 liter of a 1:1 mixture of hexane and methyl-t-butyl ester. The resulting mixture was filtered and dried.
  • the synthesis product thus obtained was purified by column chromatography to give Exemplified Monomer (4).
  • the isolated N- ⁇ 4-[(2-pyrinidinylamino)sulfonyl]phenyl ⁇ acetamide was dissolved in 2.5 liter of a 1:1 mixture of ethanol and 1-methoxy-2-propanol. Thereto, 105 g (2.66 moles) of sodium hydroxide was added, and the resulting mixture was refluxed for one hour. Then, the mixture was cooled to room temperature, and the solvents were removed under reduced pressure. The reaction product was dissolved in 1,300 ml of water, and adjusted to the acidity of pH 1 by addition of concentrated hydrochloric acid. The resulting solution was cooled to 0°C. The insoluble matter was removed by filtration.
  • the water phase was extracted with three 450 ml portions of methylene chloride, and adjusted to a neutral region of pH 7 by use of a 10N sodium hydroxide solution.
  • the intermediate 4-amino-N-2-pyrimidylbenzenesulfonamide was precipitated out of the resulting water phase, so it was filtered off and dried.
  • 93.4 g of 4-amino-N-2-pyrimidylbenzenesulfonamide was obtained (yield: 70.7%).
  • Exemplified Monomers (5), (6) and (7) can also be synthesized under the reaction scheme similar to the above.
  • TRIGONOX DC50 manufactured by AkzoNobel Corporate
  • a solution prepared by dissolving 1.48 ml of TRIGONOX 141 manufactured by AkzoNobel Corporate
  • butyrolactone 3.66 ml of butyrolactone
  • the reaction vessel temperature was raised to 143°C, and thereto 1.87 ml of TRIGONOX DC50 was added over at least two hours.
  • the mixture of reactants underwent reaction for 2 hours at 140°C while being stirred at 400 rpm.
  • the temperature of the resulting reaction mixture was decreased to 120°C, and the stirring condition was increased to 500 rpm.
  • Specific Polymer (2) uses as a starting material Exemplified Monomer (1), Specific Polymer (4) Exemplified Monomer (3), Specific Polymer (5) Exemplified Monomer (7), and Specific Polymer (6) Exemplified Monomer (5).
  • Exemplified Monomer (1) Exemplified Monomer (1)
  • Specific Polymer (4) Exemplified Monomer (3) Exemplified Monomer (3)
  • Specific Polymer (5) Exemplified Monomer (7)
  • Specific Polymer (6) Exemplified Monomer (5).
  • a 250-ml reaction vessel 162 mmol of the monomer specified above as a starting material, 21.3 g (132 mmol) of benzylacetamide, 0.43 g (6 mmol) of acrylic acid and 103 g of ⁇ -butyrolactone were placed, and the resulting mixture was heated up to 140°C while being stirred at 200 rpm.
  • This reaction was conducted under a circulating current of nitrogen. After the solid matter was dissolved, the temperature of the reaction vessel was lowered to 100°C. Thereto, 0.35 ml of TRIGONOX DC50 (manufactured by AkzoNobel Corporate) and a solution prepared by dissolving 1.39 ml of TRIGONOX 141 (manufactured by AkzoNobel Corporate) in 3.43 ml of butyrolactone were added in sequence. After the initiation of reaction, the reaction vessel temperature was raised to 140°C, and thereto 1.75 ml of TRIGONOX DC50 was added over at least two hours. The mixture of reactants underwent reaction for 2 hours at 145°C while being stirred at 400 rpm.
  • Specific Polymer (3) uses as a starting material Exemplified Monomer (1), and Specific Polymer (7) Exemplified Monomer (8).
  • a 250-ml reaction vessel 132 mmol of the monomer specified above as a starting material, 25.0 g (160 mmol) of benzyl acetamide, 2.31 g (32 mmol) of acrylic acid and 104 g of ⁇ -butyrolactone were placed, and the resulting mixture was heated up to 140°C while being stirred at 200 rpm. This reaction was conducted under a circulating current of nitrogen. After the solid matter was dissolved, the temperature of the reaction vessel was lowred to 100°C.
  • An aluminum alloy which contains 0.06 mass % Si, 0.30 mass % Fe, 0.014 mass % Cu, 0.001 mass% Mn, 0.001 mass% Mg, 0.001 ,mass% Zn and 0.03 mass% Ti, the balance being Al and inevitable impurities, was used to prepare a molten metal.
  • the molten metal was then subjected to molten metal treatment, filtered and formed into an ingot of 500 mm in thickness and 1,200 mm in width by a DC casting method.
  • the ingot was soaked at 550°C for about 5 hours, and when the temperature decreased to 400°C, the ingot was formed into a rolled plate of 2.7 mm in thickness with a hot rolling mill. Then, the plate was subjected to heat treatment at 500°C with a continuous annealing device and finished with cold rolling to give a plate of 0.24 mm in thickness as an aluminum plate. This aluminum plate was formed into a plate of 1030 mm in width and then subjected to the following surface treatment.
  • the surface of the aluminum plate was subjected to mechanical surface roughening treatment with a rotating roller-shaped nylon brush while it was supplied with an aqueous suspension of an abrasive (Pumice) having a specific gravity of 1.12 as an abrasive slurry.
  • the average particle diameter of the abrasive was 8 ⁇ m, and the maximum particle diameter was 50 ⁇ m.
  • the nylon brush was made of 6 ⁇ 10 nylon, the length of the brush hair was 50 mm, and the diameter of the brush hair was 0.3 mm.
  • the nylon brush had hairs arranged densely in holes in a stainless steel cylinder of ⁇ 300 mm. Three rotating brushes were used. The distance between two supporting rollers ( ⁇ 200 nm) under the brushes was 300 mm.
  • the brush roller was pressed against the aluminum plate until the load of a driving motor for rotating the brush was increased by 7 kW relative to the load before the brush roller was pressed against the aluminum plate.
  • the direction of rotation of the brush was the same as the direction of movement of the aluminum plate.
  • the number of revolutions of the brush was 200 rpm.
  • the aluminum plate obtained above was subjected to etching treatment by spraying with an aqueous solution of sodium hydroxide at a concentration of 2.6 mass% and aluminum ions at a concentration of 6.5 mass% at a temperature of 70°C, whereby the aluminum plate was dissolved in an amount of 10 g/m 2 . Thereafter, the aluminum plate was washed by spraying with water.
  • the aluminum plate was subjected to desmut treatment with an aqueous solution (containing 0.5 mass% aluminum ion) of 1 mass% nitric acid at a temperature of 30°C and then washed by spraying with water.
  • the aqueous solution of nitric acid used in the desmut treatment was waste liquid resulted from the process of electrochemical surface roughening treatment with an alternating current in an aqueous solution of nitric acid.
  • the plate was subjected to continuous electrochemical surface roughening treatment with an alternating voltage of 60 Hz.
  • the electrolyte used was 10.5 g/L aqueous nitric acid solution (containing 5 g/L aluminum ion and 0.007 mass% ammonium ion) at a temperature of 80°C.
  • the electrochemical surface roughening treatment was carried out with a carbon electrode as a counter electrode wherein the alternating current power source waveform had a waveform as shown in Fig. 1 , the time required for the electric current to reach from 0 to the peak was 0.8 msec., the duty ratio was 1 : 1, and a trapezoidal rectangular wave alternating current was used. Ferrite was used as an auxiliary anode.
  • the electrolyte chamber used was as shown in Fig. 2 .
  • 11 denotes an aluminum plate
  • 12 denotes a radial drum roller
  • 13a and 13b each denote a main electrode
  • 14 denotes an electrolytic treatment liquid
  • 15 denotes an electrolytic liquid supplying opening
  • 16 denotes a slit
  • 17 denotes an electrolytic liquid passage
  • 18 denotes an auxiliary anode
  • 19a and 19b each denote a thyristor
  • 20 denotes an alternating current power supply
  • 40 denotes a main electrolytic bath
  • 50 denotes an auxiliary anode bath.
  • the current density was 30 A/dm 2 in terms of the electric current peak, and the electrical quantity was 220 C/dm 2 in terms of the total electrical quantity when the aluminum plate was an anode. 5% of the electric current from the power source was fed through the auxiliary anode. Thereafter, the plate was washed by spraying with water.
  • the aluminum plate was subjected to etching treatment by spraying with an aqueous solution of sodium hydroxide at a concentration of 26 mass% and aluminum ions at a concentration of 6.5 mass% at a temperature of 32°C, whereby the aluminum plate was dissolved in an amount of 0.20 g/m 2 .
  • Smut components composed in the main of aluminum hydroxide formed by the electrochemical surface roughening treatment using the alternating current in the previous stage, were removed, and the edges of the pits formed were dissolved to smooth the edge. Thereafter, washing by spraying with water was carried out.
  • the aluminum plate was subjected to desmut treatment with an aqueous solution of 25 mass% nitric acid (containing 0.5 mass% aluminum ions) at a temperature of 30°C and then washed by spraying with water.
  • Anodizing treatment was carried out with an anodizing apparatus for two-step current feeding which has a structure with first and second electrolyte zones of 6 m in length each, first and second current feeding zones of 3 m in length, and first and second current feeding zones of 2.4 m in length.
  • the electrolytes supplied to the first and second electrolytic zones were sulfuric acid. Both the electrolytes were 170 g/L sulfuric acid (containing 0.5 mass% aluminum ions) at a temperature of 43°C. Thereafter, washing by spraying with water was carried out. The final anodized coating was 2.7 g/m 2 .
  • the aluminum support obtained by the anodizing treatment was subjected to alkali metal silicate treatment (silicate treatment) by dipping it in a treatment bath of 1 mass% aqueous sodium silicate No. 3 at a temperature of 30 °C for 10 seconds. Thereafter, the aluminum support was washed by spraying with water
  • the resulting aluminum support was coated with an undercoat liquid having the following formulation and then dried at 80 °C for 15 seconds, to form a coating thereon.
  • the amount of the coating (undercoat layer) after drying was 15 mg/m 2 .
  • the coating liquid for the lower recording layer having the following formulation was applied to the thus obtained support such that the application amount thereof was 0.85 g/m 2 , and then dried at 140°C for 50 seconds with PERFECT OVEN PH200 (trade name, manufactured by TABAI) by setting the level of wind control thereof to seven. Thereafter, the following coating liquid for the upper recording layer having the following formulation was applied to the resulting coating film such that the application amount thereof was 0.15 g/m 2 , and then dried at 120°C for 1 minute, so as to provide planographic printing plate precursors of Examples 1 to 9 and Comparative Examples 1 to 3.
  • Each of the planographic printing plate precursors obtained in Examples 1 to 9 and Comparative Examples 1 to 3 was cut with a microtome or the like to make a cross section of the recording layer, and conductivity was given to the cross section. Then, electron microphotographs of the cross section were taken by means of a scanning electron microscope (SEM), and observations thereof were carried out. As observation results, it was found that a dispersion phase was present in each of the lower recording layers in Examples 1 to 9 and Comparative Example 3. The size of each dispersion phase was in a range of 0.05 ⁇ m to 0.55 ⁇ m. On the other hand, the lower recording layers in Comparative Examples 1 and 2 were homogeneous layers, and therein no dispersion phase was observed.
  • Droplets of the test solutions 1 to 3 in a volume of 40 ⁇ L on an individual basis were allowed to fall on different positions of the recording layer surface, respectively, in each of the planographic printing plate precursors obtained. After a lapse of 3 minutes, the droplets were wiped off the recording layer surface by means of cotton pads. Damages to the recording layer caused by the test solutions were checked by visual observations, and evaluated on the following criteria.
  • planographic printing plate precursors of Examples 1 to 9 are superior in all of the fine-line image reproducibility, printing durability and chemical resistance as compared with the planographic printing plate precursors of Comparative Examples 1 and 2 whose lower layers form no dispersion phase and the planographic printing plate precursor of Comparative Example 3 wherein the resin included in the dispersion phase of the lower layer has a higher rate of dissolution in an aqueous alkali solution than the resin included in the matrix phase has.

Landscapes

  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Thermal Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials For Photolithography (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)

Claims (7)

  1. Flachdruckplattenvorläufer, umfassend:
    einen Träger; und
    zwei oder mehr positive Aufzeichnungsschichten, die jeweils ein Harz und einen Infrarotabsorber umfassen, wobei jede der Schichten eine Löslichkeit in Bezug auf eine wässrige Alkalilösung aufweist, die durch Belichtung mit Infrarotlaserlicht erhöht wird, worin:
    von den zwei oder mehr positiven Aufzeichnungsschichten die positive Aufzeichnungsschicht, die sich am nähesten zum Träger befindet, zwei Harze umfasst;
    mindestens eines der zwei Harze ein Polymer ist, das mindestens eine Struktureinheit umfasst, die ausgewählt ist aus einer durch die folgende Formel (I) dargestellten Struktureinheit und einer durch die folgende Formel (II) dargestellten Struktureinheit;
    eines der zwei Harze in einer Dispersionsphase enthalten ist, die in einer Matrixphase dispergiert ist, worin die mittlere Hauptachse der Dispersionsphase 0,05 bis 0,6 µm beträgt;
    worin die Matrixphase als ein Dispersionsmedium dient und das andere der zwei Harze umfasst; und
    die Auflösungsgeschwindigkeit bezüglich einer wässrigen alkalischen Lösung des Harzes, das in der Dispersionsphase enthalten ist, kleiner ist als die des Harzes, das in der Matrixphase enthalten ist;
    Figure imgb0059
    Figure imgb0060
    worin in den Formeln (I) und (II) R1 ein Wasserstoffatom oder eine Alkylgruppe darstellt; Z -O- oder NR2 darstellt; R2 ein Wasserstoffatom, eine Alkylgruppe, eine Alkenylgruppe oder eine Alkinylgruppe darstellt; Ar1 und Ar2 jeweils unabhängig eine aromatische Gruppe darstellen; mindestens eines von Ar1 und Ar2 eine heteroaromatische Gruppe ist; und a und b jeweils unabhängig 0 oder 1 bezeichnen.
  2. Flachdruckplattenvorläufer gemäß Anspruch 1, worin in den Formeln (I) und (II) R1 ein Wasserstoffatom oder eine Methylgruppe ist.
  3. Flachdruckplattenvorläufer gemäß Anspruch 1 oder 2, worin in den Formeln (I) und (II) R1 eine Methylgruppe ist.
  4. Flachdruckplattenvorläufer gemäß irgendeinem der Ansprüche 1 bis 3, worin in den Formeln (I) und (II) jedes von a und b 1 ist.
  5. Flachdruckplattenvorläufer gemäß irgendeinem der Ansprüche 1 bis 4, worin mindestens eines der zwei Harze in Wasser unlöslich und in einer wässrigen Alkalilösung löslich ist.
  6. Flachdruckplattenvorläufer gemäß Anspruch 5, worin die Matrixphase das eine der zwei Harze umfasst, das in Wasser unlöslich und in einer wässrigen Alkalilösung löslich ist.
  7. Flachdruckplattenvorläufer gemäß irgendeinem vorhergehenden Anspruch, worin das Polymer, das mindestens eine Struktureinheit umfasst, die ausgewählt ist aus einer durch die Formel (I) dargestellte Struktureinheit und einer durch die Formel (II) dargestellten Struktureinheit, in der Matrixphase der Aufzeichnungsschicht am nächsten zum Träger enthalten ist und das Masseverhältnis des Polymers zu dem Harz, das in der Dispersionsphase enthalten ist, von 90:10 bis 60:40 beträgt.
EP09150845.7A 2008-01-21 2009-01-19 Flachdruckplattenvorläufer Not-in-force EP2080616B1 (de)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2008010935A JP2009175195A (ja) 2008-01-21 2008-01-21 平版印刷版原版

Publications (2)

Publication Number Publication Date
EP2080616A1 EP2080616A1 (de) 2009-07-22
EP2080616B1 true EP2080616B1 (de) 2013-11-27

Family

ID=40561928

Family Applications (1)

Application Number Title Priority Date Filing Date
EP09150845.7A Not-in-force EP2080616B1 (de) 2008-01-21 2009-01-19 Flachdruckplattenvorläufer

Country Status (2)

Country Link
EP (1) EP2080616B1 (de)
JP (1) JP2009175195A (de)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2213690B1 (de) * 2009-01-30 2015-11-11 Agfa Graphics N.V. Neues alkalisches lösliches harz
EP2555054B1 (de) * 2010-03-31 2018-06-20 FUJIFILM Corporation Verfahren zur herstellung einer lithographischen druckplatte und druckverfahren
JP5662832B2 (ja) 2010-08-31 2015-02-04 富士フイルム株式会社 画像形成材料、平版印刷版原版及び平版印刷版の作製方法
JP5241871B2 (ja) 2011-03-11 2013-07-17 富士フイルム株式会社 サーマルポジ型平版印刷版原版及び平版印刷版の作製方法
EP2796929B1 (de) 2011-03-31 2015-12-30 Fujifilm Corporation Lithographiedruckplattenvorläufer und Verfahren zur Herstellung davon
US8771920B2 (en) 2011-03-31 2014-07-08 Fujifilm Corporation Lithographic printing plate precursor and method of preparing the same
JP5301015B2 (ja) 2011-07-25 2013-09-25 富士フイルム株式会社 感光性平版印刷版原版及び平版印刷版の作製方法
JP5624003B2 (ja) 2011-09-13 2014-11-12 富士フイルム株式会社 平版印刷版の製造方法及び平版印刷版
JP2013218315A (ja) * 2012-03-13 2013-10-24 Fujifilm Corp 平版印刷版原版及び平版印刷版の作製方法
JP5490168B2 (ja) * 2012-03-23 2014-05-14 富士フイルム株式会社 平版印刷版原版及び平版印刷版の作製方法
JPWO2018003405A1 (ja) 2016-06-29 2019-01-10 富士フイルム株式会社 ポジ型感光性樹脂組成物、ポジ型平版印刷版原版、及び、平版印刷版の作製方法
WO2018061511A1 (ja) * 2016-09-29 2018-04-05 富士フイルム株式会社 ポジ型平版印刷版原版、及び、平版印刷版の作製方法
JP2020064082A (ja) 2017-02-17 2020-04-23 富士フイルム株式会社 ポジ型平版印刷版原版、及び、平版印刷版の作製方法

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6294311B1 (en) * 1999-12-22 2001-09-25 Kodak Polychrome Graphics Llc Lithographic printing plate having high chemical resistance
JP2005242241A (ja) 2004-02-27 2005-09-08 Fuji Photo Film Co Ltd 平版印刷版原版
JP2005352270A (ja) * 2004-06-11 2005-12-22 Fuji Photo Film Co Ltd 平版印刷版原版
JP2006003658A (ja) * 2004-06-17 2006-01-05 Fuji Photo Film Co Ltd 平版印刷版原版
JP4474309B2 (ja) 2005-03-22 2010-06-02 富士フイルム株式会社 平版印刷版原版及びその作製方法
ES2365930T3 (es) * 2006-02-28 2011-10-13 Agfa Graphics N.V. Un precursor de plancha de impresión litográfica que funciona como positivo sensible al calor.
DE602006004839D1 (de) 2006-02-28 2009-03-05 Agfa Graphics Nv Positiv arbeitende Lithografiedruckformen
JP4890403B2 (ja) 2007-09-27 2012-03-07 富士フイルム株式会社 平版印刷版原版

Also Published As

Publication number Publication date
EP2080616A1 (de) 2009-07-22
JP2009175195A (ja) 2009-08-06

Similar Documents

Publication Publication Date Title
EP2080616B1 (de) Flachdruckplattenvorläufer
US7135271B2 (en) Photosensitive composition
EP1577111B1 (de) Positiv arbeitende photoempfindliche Zusammensetzung
EP1568491B1 (de) Flachdruckplattenvorläufer
EP1705006A1 (de) Flachdruckplattenvorläufer und Verfahren zu dessen Herstellung
EP1510866B1 (de) Bildaufzeichnungsmaterial und Flachdruckplatte
EP1574331B1 (de) Flachdruckplattenvorläufer
EP2106907B1 (de) Flachdruckplattenvorläufer
WO2013137345A1 (ja) 平版印刷版原版及び平版印刷版の作製方法
US20060040205A1 (en) Planographic printing plate precursor
EP2644379B1 (de) Verfahren zur Herstellung einer Flachdruckplatte
EP2641738B1 (de) Flachdruckplattenvorläufer und Verfahren zur Herstellung einer Flachdruckplatte
EP1964675B1 (de) Infrarot-Laser-empfindlicher Flachdruckplattenvorläufer
EP2042310B1 (de) Flachdruckplattenvorläufer
EP2042308B1 (de) Flachdruckplattenvorläufer
EP1640173B1 (de) Flachdruckplattenvorläufer.
EP2042305B1 (de) Flachdruckplattenvorläufer
JP2010078686A (ja) 平版印刷版原版
JP2005352270A (ja) 平版印刷版原版

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA RS

17P Request for examination filed

Effective date: 20091120

AKX Designation fees paid

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK TR

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20130619

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 642513

Country of ref document: AT

Kind code of ref document: T

Effective date: 20131215

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602009020360

Country of ref document: DE

Effective date: 20140123

REG Reference to a national code

Ref country code: NL

Ref legal event code: VDEP

Effective date: 20131127

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 642513

Country of ref document: AT

Kind code of ref document: T

Effective date: 20131127

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140327

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20131127

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20131127

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140227

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20131127

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20131127

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20131127

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20131127

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20131127

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20131127

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20131127

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20131127

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140327

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20131127

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602009020360

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140119

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20131127

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20131127

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20131127

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20131127

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20131127

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20131127

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20140131

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20140131

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20140930

26N No opposition filed

Effective date: 20140828

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20140131

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602009020360

Country of ref document: DE

Effective date: 20140828

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20140119

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20131127

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20131127

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20131127

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140228

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20131127

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20131127

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20090119

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20180117

Year of fee payment: 10

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20131127

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20190108

Year of fee payment: 11

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20190119

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190119

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602009020360

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200801