WO2019130547A1 - Procédé d'impression pour cliché original de plaque d'impression à plat et appareil d'impression pour cliché original de plaque d'impression à plat - Google Patents

Procédé d'impression pour cliché original de plaque d'impression à plat et appareil d'impression pour cliché original de plaque d'impression à plat Download PDF

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WO2019130547A1
WO2019130547A1 PCT/JP2017/047234 JP2017047234W WO2019130547A1 WO 2019130547 A1 WO2019130547 A1 WO 2019130547A1 JP 2017047234 W JP2017047234 W JP 2017047234W WO 2019130547 A1 WO2019130547 A1 WO 2019130547A1
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Prior art keywords
plate precursor
printing plate
group
information
printing
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PCT/JP2017/047234
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English (en)
Japanese (ja)
Inventor
昌隆 植田
慶彦 黒川
小林　清隆
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富士フイルムグローバルグラフィックシステムズ株式会社
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Priority to PCT/JP2017/047234 priority Critical patent/WO2019130547A1/fr
Publication of WO2019130547A1 publication Critical patent/WO2019130547A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C1/00—Forme preparation
    • B41C1/055—Thermographic processes for producing printing formes, e.g. with a thermal print head
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
    • B41N1/00—Printing plates or foils; Materials therefor
    • B41N1/12—Printing plates or foils; Materials therefor non-metallic other than stone, e.g. printing plates or foils comprising inorganic materials in an organic matrix
    • B41N1/14—Lithographic printing foils

Definitions

  • the present invention relates to a printing method for a lithographic printing plate precursor and a printing apparatus for a lithographic printing plate precursor.
  • lithographic printing plate precursors are currently being obtained by a CTP (Computer to Plate) system.
  • CTP Computer to Plate
  • a lithographic printing plate precursor is exposed by imagewise exposing the lithographic printing plate precursor directly using a solid laser or a semiconductor laser diode based on printing data, and then removing non-image areas by development. It has gained.
  • the lithographic printing plate precursor obtained in this manner is mounted on a plate cylinder of a printing press, and printing is performed on printing paper.
  • on-machine development In recent years, a method called "on-machine development” has been proposed in order to reduce environmental load such as waste liquid treatment associated with development processing.
  • on-press development after the imagewise exposure of the lithographic printing plate precursor, conventional development is not performed, the lithographic printing plate precursor is mounted on the plate cylinder of the printing machine, and the non-image area is removed by dampening water or the like.
  • the above-mentioned planographic printing plate precursor for on-press development is mounted on a plate cylinder of a printing machine in a state of being imagewise exposed. Since the difference in density between the image area and the non-image area of the lithographic printing plate precursor, that is, the density difference between the exposed area and the non-exposed area, is small in the imagewise exposed state, the lithographic printing plate precursor prepared through development processing Compared to, its plate-making is more difficult. Therefore, there is a concern that the lithographic printing plate precursor may be erroneously attached when attached to the plate cylinder of the printing press.
  • Patent Document 1 the mounting cylinder position information on a plate cylinder is marked on the surface of a lithographic printing plate precursor by an ink jet recording method using an aqueous ink containing an aqueous dye and an aqueous fixing agent, and this marking is performed.
  • Patent Document 2 discloses that, after exposing a lithographic printing plate precursor for on-press development, the printing plate information is printed directly on the lithographic printing plate precursor.
  • Patent Document 1 is directed to a printing plate, that is, a lithographic printing plate precursor produced by imagewise exposing and developing a lithographic printing plate precursor.
  • Patent Document 1 does not prevent erroneous mounting when mounting an imagewise exposed lithographic printing plate precursor on a plate cylinder of a printing machine with respect to a lithographic printing plate precursor for on-press development.
  • Patent Document 2 adds plate information by printing directly on a lithographic printing plate precursor based on the information of the information management server. Therefore, it is necessary to ensure that the added plate information matches the plate image of the lithographic printing plate precursor. Therefore, the whole system becomes large and complicated.
  • the present invention has been made in view of such circumstances, and a method of printing on a lithographic printing plate precursor capable of printing plate information on a lithographic printing plate precursor for on-press development, and a lithographic printing plate precursor for on-press development It is an object of the present invention to provide a printing apparatus.
  • a method of printing on a lithographic printing plate precursor is a lithographic printing plate precursor comprising an exposed portion by imagewise exposure and a non-exposed portion, which is between the exposed portion and the non-exposed portion
  • E E ((L2 * -L1 * ) 2 + (a2 * -a1 * ) 2 + (b1 * -b2 * ) 2 ) 1/2
  • L1 * , a1 * , and b1 * represent values in the exposed area
  • L2 * , a2 * , and b2 * represent values in the non-exposed area.
  • printing in the printing step is performed by an ink jet recording method using an ink containing a dye.
  • the dye is a carbonium dye.
  • the carbonium dye is at least one selected from the group of diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, and acridine dyes.
  • the carbonium dye is a triphenylmethane dye.
  • the triphenylmethane dye is a triamino dye.
  • the first information is irradiated with light having a wavelength of 620 nm or more and 750 nm or less to detect reflected light of the light.
  • a printing apparatus for a lithographic printing plate precursor includes an exposed portion and a non-exposed portion by imagewise exposure, and L determined by the following equation between the exposed portion and the non-exposed portion
  • a processing unit for converting the first electronic information into the second electronic information, a printing unit for printing the second information on the lithographic printing plate precursor based on the second electronic information, and a transmission of the first electronic information from the imaging unit to the processing unit
  • E E ((L2 * -L1 * ) 2 + (a2 * -a1 * ) 2 + (b1 * -b2 * ) 2 ) 1/2
  • L1 * , a1 * , and b1 * represent values in the exposed area
  • L2 * , a2 * , and b2 * represent values in the non-exposed area.
  • the present invention by reading the first information printed on the planographic printing plate precursor, it is possible to print the second information which is the plate information on the planographic printing plate precursor for on-press development.
  • FIG. 1 is a conceptual view of a CTP system including a printing apparatus for a lithographic printing plate precursor.
  • 1 is a plan view of a lithographic printing plate precursor after imagewise exposure. It is the elements on larger scale of 1st information.
  • It is a conceptual diagram of 2nd information. It is a top view of the lithographic printing plate precursor after printing 2nd information.
  • FIG. 1 is a flowchart of a printing method on a lithographic printing plate precursor.
  • the method of printing on a lithographic printing plate precursor includes a lithographic printing plate precursor preparing step (step S1), an imaging step (step S2), a processing step (step S3), and a printing step (step S4). At least.
  • an L * a * b * color space between the exposed portion and the non-exposed portion, which includes the exposed portion and the non-exposed portion by imagewise exposure is obtained by the following equation
  • a lithographic printing plate precursor for on-press development having a color difference ⁇ E of 2 or more and 8 or less is prepared.
  • E E ((L2 * -L1 * ) 2 + (a2 * -a1 * ) 2 + (b1 * -b2 * ) 2 ) 1/2
  • L1 * , a1 * , and b1 * represent values in the exposed area
  • L2 * , a2 * , and b2 * represent values in the non-exposed area.
  • the imaging step (step S2) first information including an exposed portion and a non-exposed portion is converted into first electronic information.
  • the processing step (step S3) the first electronic information is converted into second electronic information.
  • the printing step (step S4) includes a printing step of printing the second information on the lithographic printing plate precursor based on the second electronic information.
  • Step S1 ⁇ Planar Printing Plate Precursor Preparation Step (Step S1)>
  • an L * a determined by the following equation between the exposed portion and the non-exposed portion including the exposed portion and the non-exposed portion by imagewise exposure
  • a lithographic printing plate precursor for on-press development having a color difference ⁇ E in the * b * color space of 2 or more and 8 or less is prepared.
  • E E ((L2 * -L1 * ) 2 + (a2 * -a1 * ) 2 + (b1 * -b2 * ) 2 ) 1/2
  • L1 * , a1 * , and b1 * represent values in the exposed area
  • L2 * , a2 * , and b2 * represent values in the non-exposed area.
  • the planographic printing plate precursor for on-press development has at least a support and an image recording layer.
  • the lithographic printing plate precursor has, if necessary, an undercoat layer (sometimes referred to as an intermediate layer) between the support and the image recording layer, and a protective layer (sometimes referred to as an overcoat layer) on the image recording layer.
  • the planographic printing plate precursor for on-press development refers to a planographic printing plate precursor having an image recording layer in which the non-image area can be removed by at least one of printing ink and dampening water on a printing press.
  • a well-known support is used as a support of a lithographic printing plate precursor.
  • an aluminum plate is preferable as a support.
  • the aluminum plate used for the support is preferably subjected to surface treatment such as roughening treatment or anodizing treatment prior to use.
  • Roughening treatment of the surface of the aluminum plate is performed by various methods. For example, mechanical roughening treatment, electrochemical roughening treatment (roughening treatment that dissolves the surface electrochemically), chemical roughening treatment (roughening treatment that selectively dissolves the surface chemically) Etc.).
  • the methods described in paragraphs [0241] to [0245] of JP-A-2007-206217 can be preferably applied.
  • sulfuric acid anodization and phosphoric acid anodization are mentioned, for example.
  • the anodic pore size in the case of sulfuric acid anodization is typically less than 20 nm, whereas the anodic pore size in the case of phosphoric acid anodization is typically more than 30 nm.
  • Other conventional anodization methods can also be used, such as methods that yield anode pore sizes larger than the anode pore size formed by sulfuric acid anodization.
  • a method of anodizing an aluminum plate for example in a mixture of acids (for example a mixture of phosphoric acid and sulfuric acid), using a combination of acids, or sequentially anodizing using two or more acids (for example phosphorus Acid anodization followed by sulfuric acid anodization or vice versa is also suitable.
  • a mixture of acids for example a mixture of phosphoric acid and sulfuric acid
  • sequentially anodizing using two or more acids for example phosphorus Acid anodization followed by sulfuric acid anodization or vice versa is also suitable.
  • the support preferably has a center line average roughness of 0.10 to 1 from the viewpoint of good adhesion to an undercoat layer formed thereon or an image recording layer, good printing durability, and good stain resistance. It is preferable that it is .2 ⁇ m.
  • the color density of the support is preferably from 0.15 to 0.65 in terms of reflection density value from the viewpoint of good image forming property by antihalation at the time of imagewise exposure and good plate inspection property after development.
  • the thickness of the support is preferably 0.1 to 0.6 mm, more preferably 0.15 to 0.4 mm, and still more preferably 0.2 to 0.3 mm.
  • a support that has been subjected to surface treatment such as roughening treatment or anodizing treatment in order to improve the hydrophilicity of the non-image area and to prevent printing stains. It is also preferable to further subject the surface to a hydrophilization treatment.
  • the support is treated with an alkali metal silicate which is subjected to immersion treatment or electrolytic treatment in an aqueous solution such as sodium silicate, treated with potassium fluorozirconate, and treated with polyvinyl phosphonic acid.
  • an aqueous solution such as sodium silicate, treated with potassium fluorozirconate, and treated with polyvinyl phosphonic acid.
  • the method etc. are mentioned and the method of immersing in polyvinyl phosphonic acid aqueous solution is used preferably.
  • the image recording layer of the lithographic printing plate precursor for on-press development is an image in which the non-exposed area which is the non-image area is removed by at least one of printing ink and neutral to alkaline dampening water on a printing press It is a recording layer.
  • the image recording layer according to the present embodiment preferably contains an infrared absorber, a polymerizable initiator, a polymerizable compound, and a binder polymer.
  • the dampening solution preferably has a pH of 7-11.
  • the infrared absorber has a function of converting the absorbed infrared ray into heat and a function of being excited by the infrared ray to perform electron transfer and / or energy transfer to a polymerization initiator described later.
  • the infrared absorbing agent used in the present embodiment is preferably a dye or a pigment having an absorption maximum at a wavelength of 760 to 1200 nm, more preferably a dye.
  • dyes such as azo dyes, metal complex salt azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, cyanine dyes, squarylium dyes, pyrylium salts, metal thiolate complexes, etc. Can be mentioned.
  • cyanine dyes particularly preferred are cyanine dyes, squarylium dyes, pyrylium salts, nickel thiolate complexes, and indolenine cyanine dyes. Furthermore, cyanine dyes and indolenine cyanine dyes are preferable, and as a particularly preferable example, cyanine dyes represented by the following general formula (a) can be mentioned.
  • X 1 represents a hydrogen atom, a halogen atom, -N (R 9 ) (R 10 ), -X 2 -L 1 or a group shown below.
  • R 9 and R 10 may be the same as or different from each other, and may be a substituted aryl group having 6 to 10 carbon atoms, an alkyl group having 1 to 8 carbon atoms, a hydrogen atom And R 9 and R 10 may combine with each other to form a ring.
  • preferred is a phenyl group (-NPh 2 ).
  • X 2 represents an oxygen atom or a sulfur atom
  • L 1 represents a hydrocarbon group having 1 to 12 carbon atoms, a heteroaryl group, or a hydrocarbon group having 1 to 12 carbon atoms including a hetero atom.
  • hetero atom shows N, S, O, a halogen atom, and Se here.
  • Xa - has Za described later - is defined as in, R a represents a hydrogen atom, an alkyl group, an aryl group, a substituted or unsubstituted amino group, and a substituted or unsubstituted amino group and a halogen atom Represent.
  • R 1 and R 2 each independently represent a hydrocarbon group having 1 to 12 carbon atoms. From the viewpoint of storage stability of the image recording layer coating solution, R 1 and R 2 are preferably hydrocarbon groups having 2 or more carbon atoms. R 1 and R 2 may be linked to each other to form a ring, and when forming a ring, it is particularly preferred to form a 5- or 6-membered ring.
  • Ar 1 and Ar 2 may be the same or different and each represent an aryl group which may have a substituent.
  • Preferred aryl groups include benzene ring and naphthalene ring.
  • Preferred examples of the substituent include a hydrocarbon group having 12 or less carbon atoms, a halogen atom, and an alkoxy group having 12 or less carbon atoms.
  • Y 1 and Y 2 which may be the same or different, each represents a sulfur atom or a dialkylmethylene group having 12 or less carbon atoms.
  • R 3 and R 4 which may be the same or different, each represent a hydrocarbon group having 20 or less carbon atoms which may have a substituent.
  • R 5 , R 6 , R 7 and R 8 which may be the same or different, each represents a hydrogen atom or a hydrocarbon group having 12 or less carbon atoms. From the availability of the raw material, preferred is a hydrogen atom.
  • Za - represents a counter anion. However, when the cyanine dye represented by the general formula (a) has an anionic substituent in its structure and charge neutralization is not required, Za - is not necessary.
  • Za - is preferably of the preservation stability of the image recording layer coating solution, a halide ion, perchlorate ion, tetrafluoroborate ion, hexafluorophosphate ion, and sulfonate ion, particularly preferably, a perchlorate ion Hexafluorophosphate ion and aryl sulfonate ion.
  • cyanine dye represented by formula (a) which can be preferably used include compounds described in paragraph Nos. [0017] to [0019] of JP-A-2001-133969, JP-A-2002-023360.
  • the particle size of the pigment is preferably 0.01 to 1 ⁇ m, and more preferably 0.01 to 0.5 ⁇ m.
  • known dispersion techniques used for ink production, toner production, etc. can be used. The details are described in "Latest Pigment Application Technology” (CMC Publishing, 1986).
  • the infrared absorber may be used alone or in combination of two or more.
  • the content of the infrared absorber is preferably 0.05 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, particularly preferably 0.2 to 10 parts by mass with respect to 100 parts by mass of the total solid content of the image recording layer. It is a mass part.
  • the polymerization initiator is a compound that initiates and accelerates the polymerization of the polymerizable compound.
  • known thermal polymerization initiators compounds having a bond with small bond dissociation energy, photopolymerization initiators and the like can be used.
  • the polymerization initiator for example, (a) organic halide, (b) carbonyl compound, (c) azo compound, (d) organic peroxide, (e) metallocene compound, (f) azide
  • examples include compounds, (g) hexaarylbiimidazole compounds, (h) organic borate compounds, (i) disulfone compounds, (j) oxime ester compounds, and (k) onium salt compounds.
  • organic halide (a) compounds described in Paragraph Nos. [0022] to [0023] of JP-A-2008-195018 are preferable.
  • the azo compound (c) for example, the azo compound described in JP-A-8-108621 can be used.
  • organic peroxide (d) for example, compounds described in paragraph [0025] of JP-A-2008-195018 are preferable.
  • azide compound (f) examples include compounds such as 2,6-bis (4-azidobenzylidene) -4-methylcyclohexanone.
  • organic borate compound (h) for example, compounds described in Paragraph No. [0028] of JP-A-2008-195018 are preferable.
  • Examples of (i) disulfone compounds include the compounds described in JP-A-61-166544.
  • onium salt compound (k) examples include S.I. I. Schlesinger, Photogr. Sci. Eng. , 18, 387 (1974), T.S. S. Bal et al, Polymer, 21, 423 (1980), a diazonium salt described in JP-A-5-158230, U.S. Pat. No. 4,069,055, ammonium described in JP-A-4-365049, etc. Salts, phosphonium salts described in U.S. Pat. Nos. 4,069,055 and 4,069,056, European Patent No. 104,143, and U.S. Patent Application Publication No. 2008/0311520 JP-A-2-150848, JP-A-2008-195018, or J. V.
  • a diphenyl iodonium salt is preferable, in particular a diphenyl iodonium salt substituted with an electron donating group such as an alkyl group or an alkoxyl group is preferable, and an asymmetric diphenyl iodonium salt is more preferable.
  • diphenyliodonium hexafluorophosphate 4-methoxyphenyl-4- (2-methylpropyl) phenyliodonium hexafluorophosphate, 4- (2-methylpropyl) phenyl-p-tolyliodonium hexafluorophosphate , 4-Hexyloxyphenyl-2,4,6-trimethoxyphenyliodonium hexafluorophosphate, 4-hexyloxyphenyl-2,4-diethoxyphenyliodonium tetrafluoroborate, 4-octyloxyphenyl-2,4 , 6-trimethoxyphenyliodonium 1-perfluorobutanesulfonate, 4-octyloxyphenyl-2,4,6-trimethoxyphenyliodonium hexafluorophosphate, bis (4-t-butyl) Eniru) iodonium tetra
  • sulfonium salts include triphenylsulfonium hexafluorophosphate, triphenylsulfonium benzoylformate, bis (4-chlorophenyl) phenylsulfonium benzoylformate, bis (4-chlorophenyl) -4-methylphenylsulfonium tetrafluoroborate And tris (4-chlorophenyl) sulfonium 3,5-bis (methoxycarbonyl) benzenesulfonate, tris (4-chlorophenyl) sulfonium hexafluorophosphate and the like.
  • organic borate compounds are preferably used.
  • the organic borate compounds include tetraphenylborate salt, tetratolylborate salt, tetrakis (4-methoxyphenyl) borate salt, tetrakis (pentafluorophenyl) borate salt, tetrakis (3,5-bis (trifluoro) (Methyl) phenyl) borate salt, tetrakis (4-chlorophenyl) borate salt, tetrakis (4-fluorophenyl) borate salt, tetrakis (2-thienyl) borate salt, tetrakis (4-phenylphenyl) borate salt, tetrakis (4-t) And -butylphenyl) borate salt, ethyl triphenyl borate salt, butyl triphenyl borate salt and the like.
  • the tetraphenyl borate salt is preferred from the viewpoints of coexistence of printing durability, tone reproducibility and stability over time.
  • Examples of the counter cation of the borate compound include known cations such as alkali metal cations, alkaline earth metal cations, ammonium cations, phosphonium cations, sulfonium cations, iodonium cations, diazonium cations and azinium cations.
  • the content of the polymerization initiator is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, and particularly preferably 0.8 to 20% by mass with respect to the total solid content of the image recording layer. Within this range, better sensitivity and better resistance to staining of non-image areas during printing can be obtained.
  • the polymerizable compound is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and is selected from compounds having at least one, preferably two or more terminal ethylenically unsaturated bonds. These have chemical forms, such as a monomer, a prepolymer, ie, a dimer, a trimer and an oligomer, or mixtures thereof, for example.
  • Examples of the monomer include unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid etc.), esters thereof and amides thereof, and preferably unsaturated carboxylic acids.
  • unsaturated carboxylic acids eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid etc.
  • addition reaction products of unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as hydroxy group, amino group and mercapto group with monofunctional or polyfunctional isocyanates or epoxies, and monofunctional or polyfunctional Dehydration condensation products with functional carboxylic acids and the like are also suitably used.
  • addition reaction products of unsaturated carboxylic acid esters or amides having an electrophilic substituent such as an isocyanate group or an epoxy group with monofunctional or polyfunctional alcohols, amines and thiols, and further halogen groups are also suitable.
  • monomers of esters of polyhydric alcohol compounds and unsaturated carboxylic acids include, as acrylic acid esters, ethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, and the like.
  • examples thereof include trimethylolpropane triacrylate, hexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol tetraacrylate, sorbitol triacrylate, ethylene oxide (EO) isocyanurate modified triacrylate, and polyester acrylate oligomer.
  • methacrylic acid esters examples include tetramethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, pentaerythritol trimethacrylate, bis [p- (3-methacryloxy-2-hydroxypropoxy) phenyl Examples include dimethylmethane, bis- [p- (methacryloxyethoxy) phenyl] dimethylmethane and the like.
  • monomers of amides of polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis-methacryl Amide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bis methacrylamide and the like.
  • urethane-based addition polymerizable compounds produced by using an addition reaction of an isocyanate and a hydroxy group are also suitable, and as such specific examples, for example, one molecule described in JP-B-48-41708.
  • tris (acryloyloxyethyl) isocyanurate, bis (acryloyloxyethyl) hydroxyethyl isocyanurate and the like from the viewpoint of being excellent in the balance of hydrophilicity related to on-press developability and polymerization ability related to printing durability.
  • isocyanuric acid ethylene oxide modified acrylates are particularly preferred.
  • the details of the method of use such as the structure of the polymerizable compound, single use or combined use, and the addition amount can be arbitrarily set according to the performance design of the final lithographic printing plate precursor.
  • the polymerizable compound is used in an amount of preferably 5 to 75% by mass, more preferably 10 to 70% by mass, and particularly preferably 15 to 60% by mass, based on the total solid content of the image recording layer.
  • the binder polymer is mainly used for the purpose of improving the film strength of the image recording layer.
  • the binder polymer conventionally known ones can be used, and polymers having film properties are preferable. Among them, acrylic resin, polyvinyl acetal resin, polyurethane resin and the like are preferable.
  • a suitable binder polymer it has a crosslinkable functional group for improving the film strength of the image portion as described in JP-A-2008-195018, in the main chain or side chain, preferably in the side chain The thing is mentioned.
  • the crosslinkable groups form crosslinks between polymer molecules to accelerate curing.
  • the crosslinkable functional group is preferably an ethylenically unsaturated group such as (meth) acrylic group, vinyl group, allyl group or styryl group, an epoxy group or the like, and the crosslinkable functional group is introduced into the polymer by polymer reaction or copolymerization.
  • a reaction of an acrylic polymer having a carboxy group in a side chain or a polyurethane with glycidyl methacrylate, or a reaction of a polymer having an epoxy group with an ethylenically unsaturated group-containing carboxylic acid such as methacrylic acid can be used.
  • the content of the crosslinkable group in the binder polymer is preferably 0.1 to 10.0 mmol, more preferably 0.25 to 7.0 mmol, particularly preferably 0.5 to 5.5 mmol per 1 g of the binder polymer. .
  • the binder polymer preferably has a hydrophilic group.
  • the hydrophilic group contributes to imparting on-press developability to the image recording layer.
  • the coexistence of the crosslinkable group and the hydrophilic group makes it possible to achieve both printing durability and on-press developability.
  • the hydrophilic group includes, for example, a hydroxy group, a carboxy group, an alkylene oxide structure, an amino group, an ammonium group, an amido group, a sulfo group, a phosphoric acid group and the like, among them an alkylene oxide unit having 2 or 3 carbon atoms. Alkylene oxide structures having 1 to 9 are preferred.
  • the binder polymer can be provided with a hydrophilic group, for example, by copolymerizing a monomer having a hydrophilic group.
  • a lipophilic group such as an alkyl group, an aryl group, an aralkyl group or an alkenyl group
  • it can carry out by copolymerizing lipophilic group containing monomers, such as an alkyl methacrylate ester.
  • the binder polymer preferably has a mass average molar mass (Mw) of 2,000 or more, more preferably 5,000 or more, and still more preferably 10,000 to 300,000.
  • the content of the binder polymer is suitably 3 to 90% by mass, preferably 5 to 80% by mass, and more preferably 10 to 70% by mass, with respect to the total solid content of the image recording layer.
  • the high molecular compound which has a polyoxyalkylene chain in a side chain is mentioned.
  • a polymer compound having a polyoxyalkylene chain in the side chain hereinafter, also referred to as a specific polymer compound
  • the permeability of dampening water is promoted and the on-press developability is improved.
  • the resin constituting the main chain of the specific polymer compound includes acrylic resin, polyvinyl acetal resin, polyurethane resin, polyurea resin, polyimide resin, polyamide resin, epoxy resin, methacrylic resin, polystyrene resin, novolac type phenol resin, polyester Resin, synthetic rubber, natural rubber and the like can be mentioned, and in particular, acrylic resin is preferable.
  • the specific polymer compound is substantially free of a perfluoroalkyl group.
  • substantially free of perfluoroalkyl groups means that the mass ratio of fluorine atoms present as perfluoroalkyl groups in the polymer compound is less than 0.5% by mass, and those that are not included are preferable. The mass ratio of fluorine atoms is measured by elemental analysis.
  • the "perfluoroalkyl group” is a group in which all hydrogen atoms of the alkyl group are substituted with a fluorine atom.
  • the alkylene oxide (oxyalkylene) in the polyoxyalkylene chain is preferably an alkylene oxide having 2 to 6 carbon atoms, more preferably ethylene oxide (oxyethylene) or propylene oxide (oxypropylene), and still more preferably ethylene oxide.
  • the number of repetition of the alkylene oxide in the polyoxyalkylene chain, ie, the poly (alkylene oxide) portion is preferably 2 to 50, and more preferably 4 to 25.
  • the number of repetitions of the alkylene oxide is 2 or more, the permeability of dampening water is sufficiently improved, and if the number of repetitions is 50 or less, the printing durability is not deteriorated due to abrasion, which is preferable.
  • the poly (alkylene oxide) moiety is preferably contained as a side chain of the polymer compound in a structure represented by the following general formula (1). More preferably, it is contained as a side chain of an acrylic resin by the structure represented by the following general formula (c).
  • y is preferably 2 to 50, more preferably 4 to 25.
  • R 13 represents a hydrogen atom or an alkyl group
  • R 14 represents a hydrogen atom or an organic group.
  • the organic group is preferably an alkyl group having a carbon number of 1 to 6, and is methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, t-butyl group, n- Examples thereof include pentyl group, isopentyl group, neopentyl group, n-hexyl group, isohexyl group, 1,1-dimethylbutyl group, 2,2-dimethylbutyl group, cyclopentyl group and cyclohexyl group.
  • R 13 is preferably a hydrogen atom or a methyl group, particularly preferably a hydrogen atom.
  • R 14 is particularly preferably a hydrogen atom or a
  • the specific polymer compound may have a crosslinkability to improve the film strength of the image area.
  • a crosslinkable functional group such as an ethylenically unsaturated bond may be introduced into the main chain or side chain of the polymer.
  • the crosslinkable functional group may be introduced by copolymerization.
  • polymer compounds having an ethylenically unsaturated bond in the main chain of the molecule include poly-1,4-butadiene, poly-1,4-isoprene and the like.
  • high molecular compounds having an ethylenically unsaturated bond in the side chain of the molecule are high molecular compounds of esters or amides of acrylic acid or methacrylic acid, which are residues of ester or amide (-COOR or CONHR Mention may be made of macromolecular compounds in which R b ) has an ethylenically unsaturated bond.
  • the specific polymer compound having crosslinkability is, for example, that the free radical (polymerization initiating radical or propagating radical of polymerization process of the polymerizable compound) is added to the crosslinkable functional group to directly or polymerize between the polymer compounds or Addition polymerization is performed via the polymerization chain of the organic compound to form a crosslink between the polymer compound molecules and cure.
  • an atom in the polymer compound for example, a hydrogen atom on a carbon atom adjacent to a functional crosslinking group
  • Crosslinks form between the compound molecules and cure.
  • the content of the crosslinkable group in the specific polymer compound is preferably 0.1 to 10.0 mmol, more preferably 1 g of the polymer compound. 1.0 to 7.0 mmol, particularly preferably 2.0 to 5.5 mmol. Within this range, good sensitivity and good storage stability can be obtained.
  • the specific polymer compound may further contain a copolymerization component for the purpose of improving various performances such as image strength, as long as the inherent effect of the specific polymer compound is not impaired.
  • a copolymerization component what is represented by the following general formula (d) can be mentioned.
  • R 18 represents a hydrogen atom or a methyl group.
  • R 19 represents a substituent.
  • Preferred examples of R 19 include an ester group, an amido group, a cyano group, a hydroxy group or an aryl group. Among them, an ester group, an amido group or a phenyl group which may have a substituent is preferable.
  • the substituent of the phenyl group include an alkyl group, an aralkyl group, an alkoxy group and an acetoxymethyl group.
  • a copolymerization component represented by general formula (d) for example, acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, N-substituted acrylamides, N-substituted methacrylamides, N, N And 2-disubstituted acrylamides, N, N-disubstituted methacrylamides, styrenes, acrylonitriles, methacrylonitriles and the like.
  • Acrylonitriles are preferred from the viewpoint of printing durability.
  • the ratio of repeating units having a poly (alkylene oxide) moiety to all repeating units constituting the specific polymer compound is not particularly limited, but is preferably 0.5 to 80 mol%, more preferably 0.5 to 50 mol. %.
  • JP-A-2015-123683 As the specific polymer compound, for example, compounds described in paragraphs [0084] to [0085] of JP-A-2015-123683 can be mentioned. However, it is not limited to these.
  • hydrophilic polymer compounds such as polyacrylic acid and polyvinyl alcohol described in JP-A-2008-195018 can be used in combination, as necessary.
  • an oleophilic polymer compound and a hydrophilic polymer compound can be used in combination.
  • the form of the specific polymer compound in the image recording layer may be present in the form of fine particles, in addition to being present as a binder which fulfills the function of connecting the components of the image recording layer.
  • the average particle size is in the range of 10 to 1000 nm, preferably in the range of 20 to 300 nm, and particularly preferably in the range of 30 to 120 nm.
  • the content of the specific polymer compound is preferably 3 to 90% by mass, more preferably 5 to 80% by mass, with respect to the total solid content of the image recording layer. In the range of 3 to 90% by mass, both the permeability of dampening water and the image forming property can be achieved more reliably.
  • a polymer compound having a polymer chain bonded to the nucleus by a sulfide bond, with a polyfunctional thiol having 6 to 10 functions as a core, and the polymer chain has a polymerizable group (Hereafter, it is also called a star-shaped polymer compound.)
  • a star-shaped polymer compound for example, compounds described in JP-A-2012-148555 can be preferably used.
  • the star polymer compound has a polymerizable group such as an ethylenically unsaturated bond for improving the film strength of the image area as described in JP-A-2008-195018, which is a main chain or a side chain, preferably a side. What has in the chain is mentioned.
  • the polymerizable groups form crosslinks between polymer molecules to accelerate curing.
  • the polymerizable group is preferably an ethylenically unsaturated group such as a (meth) acrylic group, a vinyl group, an allyl group or a styryl group, an epoxy group or the like, and the (meth) acrylic group, a vinyl group and a styryl group have a polymerization reactivity. Is more preferable in view of the (meth) acrylic group is particularly preferable. These groups can be introduced into the polymer by polymer reaction or copolymerization.
  • a reaction of a polymer having a carboxy group in a side chain with glycidyl methacrylate, or a reaction of a polymer having an epoxy group and an ethylenically unsaturated group-containing carboxylic acid such as methacrylic acid can be used. These groups may be used in combination.
  • the content of the crosslinkable group in the star polymer compound is preferably 0.1 to 10.0 mmol, more preferably 0.25 to 7.0 mmol, and most preferably 0.5 per 1 g of the star polymer compound. It is ⁇ 5.5 mmol.
  • the star polymer compound further have a hydrophilic group.
  • the hydrophilic group contributes to imparting on-press developability to the image recording layer.
  • coexistence of a polymerizable group and a hydrophilic group makes it possible to achieve both printing durability and developability.
  • R 20 and R 21 each independently represent a hydrogen atom , alkyl group, alkenyl group, .R 20 and R 21 representing an aryl group may be bonded to form a ring), -.
  • n and m each independently represent an integer of 1 to 100, and R 25 independently represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms.
  • star-shaped polymer compound is a star-shaped polymer compound having a polyoxyalkylene chain (for example, a group represented by the general formula (e) or (f)) at the side difference
  • a star-shaped polymer compound is also a polymer compound having the above-mentioned polyoxyalkylene chain in the side chain.
  • hydrophilic groups groups represented by -CONR 20 R 21 , a group represented by the general formula (e) and a group represented by the general formula (f) are preferred, and -CONR 20 R 21 and a group represented by the general formula (e) Is more preferable, and a group represented by general formula (e) is particularly preferable.
  • n is more preferably 1 to 10, and particularly preferably 1 to 4.
  • R 25 is more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, particularly preferably a hydrogen atom or a methyl group. Two or more of these hydrophilic groups may be used in combination.
  • the star polymer compound has substantially no carboxylic acid group, phosphoric acid group, and phosphonic acid group. Specifically, it is preferably less than 0.1 mmol / g, more preferably less than 0.05 mmol / g, and particularly preferably 0.03 mmol / g or less. When the content of these acid groups is less than 0.1 mmol / g, developability is further improved.
  • a lipophilic group such as an alkyl group, an aryl group, an aralkyl group or an alkenyl group can be introduced into the star polymer compound.
  • a lipophilic group-containing monomer such as alkyl methacrylate ester may be copolymerized.
  • star polymer compound examples include the compounds described in paragraphs [0101] to [0105] of JP-A-2015-123683. However, it is not limited to these.
  • the star polymer compound can be synthesized by a known method such as radical polymerization of the above-mentioned monomers constituting the polymer chain in the presence of the above-mentioned polyfunctional thiol compound.
  • the mass average molar mass (Mw) of the star polymer compound is preferably 5,000 or more and 500,000 or less, more preferably 10,000 or more and 250,000 or less, and particularly preferably 20,000 or more and 150,000 or less. Within this range, on-press developability and press life become better.
  • the star polymer compounds may be used singly or in combination of two or more. Moreover, you may use together with a normal linear-type binder polymer.
  • the content of the star polymer compound is preferably 5 to 95% by mass, more preferably 10 to 90% by mass or less, and particularly preferably 15 to 85% by mass or less based on the total solid content of the image recording layer.
  • the star polymer compound described in JP-A-2012-148555 is preferable because the permeability of dampening water is promoted and the on-press developability is improved.
  • the image recording layer may contain other components described below, as necessary.
  • the image recording layer may contain a low molecular weight hydrophilic compound in order to improve the on-press developability without reducing the printing durability.
  • hydrophilic compounds for example, as water-soluble organic compounds, glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol and the like, ethers or ester derivatives thereof, glycerin, Polyols such as pentaerythritol, tris (2-hydroxyethyl) isocyanurate, organic amines such as triethanolamine, diethanolamine and monoethanolamine and salts thereof, organic sulfones such as alkyl sulfonic acid, toluene sulfonic acid and benzene sulfonic acid Acids and their salts, organic sulfamic acids such as alkyl sulfamic acid and their salts, organic sulfuric acids such as alkyl sulfuric acid and alkyl ether sulfuric acid and their salts, phenyl phosphonic acid Organic phosphonic acids and their salts etc., tarta
  • organic sulfonate examples include those described in paragraph Nos. [0026] to [0031] of JP-A-2007-276454 and paragraph Nos. [0020] to [0047] of JP-A-2009-154525. A compound etc. are mentioned.
  • the salt may be a potassium salt or a lithium salt.
  • organic sulfate examples include the compounds described in paragraphs [0034] to [0038] of JP-A-2007-276454.
  • Preferred betaines are compounds having 1 to 5 carbon atoms in the hydrocarbon substituent to the nitrogen atom, and specific examples thereof include trimethyl ammonium acetate, dimethyl propyl ammonium acetate, 3-hydroxy-4-trimethyl.
  • the low molecular weight hydrophilic compound has a small hydrophobic part structure and hardly has a surfactant activity, so dampening water penetrates the exposed part (image part) of the image recording layer to make the hydrophobicity and film strength of the image part. It is possible to maintain the ink receptivity and the printing durability of the image recording layer without deterioration.
  • the addition amount of the low molecular weight hydrophilic compound is preferably 0.5 to 20% by mass of the total solid content of the image recording layer. 1 to 15% by mass is more preferable, and 2 to 10% by mass is more preferable. In this range, good on-press developability and press life can be obtained.
  • the compounds may be used alone or in combination of two or more.
  • an oil-receptive agent such as a phosphonium compound, a nitrogen-containing low molecular weight compound, or an ammonium group-containing polymer can be used to improve the inking property.
  • these compounds function as a surface coating agent for the inorganic stratiform compound and have an effect of preventing the decrease in the adhesion during printing by the inorganic stratiform compound.
  • Preferred examples of the phosphonium compound include phosphonium compounds described in JP-A-2006-297907 and JP-A-2007-50660. Specific examples thereof include tetrabutylphosphonium iodide, butyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, 1,4-bis (triphenylphosphonio) butanedi (hexafluorophosphate), 1,7-bis (triphenylphospho) Nio) heptane sulfate, 1,9-bis (triphenylphosphonio) nonanenaphthalene-2,7-disulfonate and the like.
  • nitrogen-containing low molecular weight compounds include compounds described in paragraphs [0021] to [0037] of JP-A 2008-284858 and paragraphs [0030] to [0057] of JP-A 2009-90645.
  • ammonium group-containing polymer any polymer having an ammonium group in its structure may be used, but a polymer containing 5 to 80 mol% of (meth) acrylate having an ammonium group in a side chain as a copolymer component is preferable.
  • polymers described in paragraph Nos. [0089] to [0105] of JP-A-2009-208458 can be mentioned.
  • the ammonium group-containing polymer is preferably in the range of 5 to 120, more preferably in the range of 10 to 110, in terms of reduced specific viscosity (unit: ml / g) determined by the following measurement method. A range of 100 is particularly preferred.
  • the above reduced specific viscosity is preferably 10000 to 150000, more preferably 17000 to 140000, and particularly preferably 20000 to 130000, in terms of mass average molar mass (Mw).
  • ⁇ Method of measuring reduction specific viscosity> 3.33 g of a 30% by weight polymer solution (1 g as solid content) are weighed into a 20 ml measuring flask and made up with N-methylpyrrolidone. The solution is allowed to stand in a thermostat at 30 ° C. for 30 minutes, placed in a Ubbelode reduced viscosity tube (viscosimeter constant 0.010 cSt / s), and the time it runs down at 30 ° C. is measured. Measurement is performed twice on the same sample, and the average value is calculated. Similarly, measurement is also performed for blank (only N-methylpyrrolidone), and the reduction specific viscosity (ml / g) is calculated from the following formula.
  • the image recording layer further contains, as other components, a surfactant, a colorant, a print-out agent, a polymerization inhibitor, a higher fatty acid derivative, a plasticizer, an inorganic fine particle, an inorganic layered compound, a co-sensitizer, A chain transfer agent etc. can be contained.
  • a surfactant e.g., a colorant, a print-out agent, a polymerization inhibitor, a higher fatty acid derivative, a plasticizer, an inorganic fine particle, an inorganic layered compound, a co-sensitizer, A chain transfer agent etc.
  • the image recording layer is prepared by dispersing or dissolving the necessary components described above in a known solvent to prepare a coating solution. This is formed by applying and drying this on a support by a known method such as bar coater application.
  • the coating amount (solid content) of the image recording layer on the support obtained after coating and drying varies depending on the application, but 0.3 to 3.0 g / m 2 is usually preferable. Within this range, good sensitivity and good film properties of the image recording layer can be obtained.
  • a subbing layer (sometimes called an intermediate layer) is preferably provided between the image recording layer and the support.
  • the undercoat layer strengthens the adhesion between the support and the image recording layer in the exposed area and facilitates the peeling of the image recording layer from the support in the unexposed area. Contribute to improve the In the case of infrared laser exposure, the undercoat layer functions as a heat insulating layer to prevent the heat generated by the exposure from diffusing to the support to reduce the sensitivity.
  • the compound used in the undercoat layer include silane coupling agents having an addition-polymerizable ethylenic double bond reactive group described in JP-A-10-282679, And phosphorus compounds having an ethylenic double bond reactive group described in JP-A-304441.
  • silane coupling agents having an addition-polymerizable ethylenic double bond reactive group described in JP-A-10-282679
  • phosphorus compounds having an ethylenic double bond reactive group described in JP-A-304441.
  • polymer compounds having an adsorptive group capable of adsorbing to the surface of a support, a hydrophilic group and a crosslinkable group are preferably mentioned.
  • a copolymer of a monomer having an adsorptive group, a monomer having a hydrophilic group, and a monomer having a crosslinkable group is preferable. More specifically, a monomer having an adsorptive group such as a phenolic hydroxy group, a carboxy group, -PO3H2, -OPO3H2, -CONHSO2-, -SO2NHSO2-, -COCH2COCH3, and a monomer having a hydrophilic group such as a sulfo group. And copolymers with monomers having a polymerizable crosslinkable group such as methacryl group and allyl group.
  • the polymer compound may have a crosslinkable group introduced by salt formation of a polar substituent of the polymer compound and a compound having a pair charge and a compound having an ethylenically unsaturated bond.
  • monomers other than the above, preferably hydrophilic monomers may be further copolymerized.
  • the content of unsaturated double bonds in the polymer compound for undercoat layer is preferably 0.1 to 10.0 mmol, more preferably 2.0 to 5.5 mmol, per 1 g of the polymer compound.
  • the weight-average molar mass of the polymer compound for undercoat layer is preferably 5,000 or more, and more preferably 10,000 to 300,000.
  • the undercoat layer contains, in addition to the above-mentioned compounds for the undercoat layer, a chelating agent, a secondary or tertiary amine, a polymerization inhibitor, a functional group having an amino group or polymerization inhibiting ability, and an aluminum support for preventing soiling over time.
  • the subbing layer is applied in a known manner.
  • the coating amount (solid content) of the undercoat layer is preferably 0.1 ⁇ 100mg / m 2, and more preferably 1 ⁇ 30mg / m 2.
  • the lithographic printing plate precursor preferably has a protective layer (overcoat layer) on the image recording layer.
  • the protective layer not only has a function of suppressing the image formation inhibition reaction by oxygen blocking, but also has a function of preventing the generation of a scratch in the image recording layer and preventing an ablation at the time of high-intensity laser exposure.
  • the protective layer having such properties is described, for example, in US Pat. No. 3,458,311 and JP-B-55-49729.
  • the low oxygen permeability polymer to be used for the protective layer either a water-soluble polymer or a water-insoluble polymer can be appropriately selected and used, and two or more types can be mixed and used as needed. it can.
  • polyvinyl alcohol, modified polyvinyl alcohol, polyvinyl pyrrolidone, a water-soluble cellulose derivative, poly (meth) acrylonitrile and the like can be mentioned.
  • modified polyvinyl alcohol an acid-modified polyvinyl alcohol having a carboxy group or a sulfo group is preferably used. Specifically, modified polyvinyl alcohol described in JP 2005-250216 A and JP 2006-259137 A is preferable.
  • the protective layer preferably contains an inorganic stratiform compound such as natural mica or synthetic mica as described in JP-A-2005-119273 in order to enhance the oxygen blocking property.
  • an inorganic stratiform compound such as natural mica or synthetic mica as described in JP-A-2005-119273 in order to enhance the oxygen blocking property.
  • polysaccharides in the protective layer.
  • starch derivatives for example, dextrin, enzyme-degraded dextrin, hydroxypropylated starch, carboxymethylated starch, phosphated starch, polyoxyalkylene grafted starch, cyclodextrin
  • celluloses for example, carboxymethylcellulose, carboxy Ethyl cellulose, methyl cellulose, hydroxypropyl cellulose, methyl propyl cellulose etc.
  • carrageenan alginic acid, guar gum, locust bean gum, xanthan gum, gum arabic, soybean polysaccharide etc.
  • starch derivatives such as polyoxyalkylene grafted starch, gum arabic, carboxymethylcellulose, soybean polysaccharide and the like are preferably used.
  • the polysaccharide is preferably used in the range of 1 to 20% by mass with respect to the solid content of the protective layer.
  • the protective layer can contain known additives such as a plasticizer for imparting flexibility, a surfactant for improving the coating property, and an inorganic fine particle for controlling the slipperiness of the surface.
  • a plasticizer for imparting flexibility such as acrylic acid, acrylic acid, and a surfactant for improving the coating property.
  • an inorganic fine particle for controlling the slipperiness of the surface such as silicone oil, silicone oil, and a surfactant for improving the coating property.
  • an inorganic fine particle for controlling the slipperiness of the surface.
  • the protective layer is applied in a known manner.
  • the coating amount of the protective layer is a coating amount after drying is preferably 0.01 ⁇ 10g / m 2, more preferably 0.02 ⁇ 3g / m 2, particularly preferably 0.02 ⁇ 1g / m 2.
  • Imagewise exposure is performed on the above-mentioned planographic printing plate precursor for on-press development, and an exposed portion and a non-exposed portion are formed on the planographic printing plate precursor.
  • the imagewise exposure is preferably performed by laser exposure through a transparent original having a line image, halftone dot image or the like, or by laser light scanning with digital data.
  • the wavelength of the light source is preferably 700 to 1400 nm.
  • a solid-state laser and a semiconductor laser emitting infrared rays are preferable.
  • the output is preferably 100 mW or more
  • the exposure time per pixel is preferably 20 microseconds or less
  • the irradiation energy amount is preferably 10 to 300 mJ / cm 2 . It is preferred to use a multi-beam laser device to reduce the exposure time.
  • the exposure mechanism may be any of an inner drum system, an outer drum system, a flat bed system, and the like.
  • Imagewise exposure can be performed by a conventional method using a computer to plate (CTP) apparatus (also referred to as a platesetter) or the like.
  • CTP computer to plate
  • FIG. 2 is a conceptual view of a CTP system including a CTP device.
  • the CTP system 1 includes a RIP device 10, a CTP device 20, and a stocker 30.
  • the printing system including the CTP system 1 further includes an information management server (not shown) and a client computer.
  • the order information number, JOBID (work identification number), customer information, color plate name, screen type, sheet name, sheet size and the like are input to the information management server, and a print instruction is issued.
  • JOBID work identification number
  • customer information color plate name, screen type, sheet name, sheet size and the like
  • a print instruction is issued.
  • an image, a document, etc. are edited to produce so-called image information.
  • plate information required for mounting on a printing machine is input to the client computer.
  • the image information and the plate information produced by the client computer are input to the RIP device 10.
  • the RIP unit 10 converts the image information and the plate information into a raster image.
  • Print information including image information and plate information, which has been converted into a raster image, is input to the CTP device 20.
  • the CTP device 20 includes an exposure mechanism, and the exposure mechanism performs imagewise exposure on the lithographic printing plate precursor based on the input printing information. The exposed portion and the non-exposed portion are formed on the lithographic printing plate precursor by the imagewise exposure with the CTP device 20.
  • the version information can be added not only from the client computer but also using the function of the RIP device 10.
  • the infrared absorber When the image recording layer of the lithographic printing plate precursor is exposed, the infrared absorber is excited from the HOMO (Highest Occupied Molecular Orbital) to the LUMO (Lowest Unoccupied Molecular Orbital) at the exposed portion, Color.
  • HOMO Highest Occupied Molecular Orbital
  • LUMO Low Unoccupied Molecular Orbital
  • the lithographic printing plate precursor 2 after the imagewise exposure is discharged from the CTP device 20.
  • the exposed area is colored and the non-exposed area is not colored, so the color difference ⁇ E in the L * a * b * color space between the exposed area and the non-exposed area is 2 or more It will be 8 or less.
  • the L * a * b * color space is a color system for representing the color of an object, standardized by the International Commission on Illumination (CIE), and also defined in JIS Z8781-4: 2013. In the L * a * b * color space, L * indicates lightness and a * b * indicates hue and saturation.
  • the color difference ⁇ E in the L * a * b * color space between the exposed portion and the non-exposed portion is 2 or more and 8 or less, it becomes possible to recognize the exposed portion and the non-exposed portion.
  • the color difference ⁇ E between the exposed portion and the non-exposed portion can be measured, for example, by a color difference meter (SpectroEye manufactured by X-Rite).
  • Step S2 ⁇ Imaging Process (Step S2)>
  • first information including an exposed portion and a non-exposed portion is converted into first electronic information.
  • the CTP device 20 includes an imaging unit 40 that images the exposed surface of the discharged lithographic printing plate precursor 2.
  • the imaging unit 40 includes an imaging element, and the imaging element converts light into an electrical signal.
  • a CCD (Charge-Coupled Device) image sensor and a CMOS (Complementary MOS) image sensor can be applied as an imaging element.
  • the imaging unit 40 may be a line system in which imaging elements are arranged in a line, or an area system in which imaging elements are two-dimensionally arranged.
  • a CCD method and a CIS (Contact Image Sensor) method may be used.
  • the CCD method light reflected from an object is reflected using a mirror, collected using a plurality of lenses, and then read.
  • the CIS system a mirror is not provided, and reflected light from an object is directly read by a sensor.
  • FIG. 3 is a plan view of the lithographic printing plate precursor 2 after imagewise exposure. As shown in FIG. 3, when the imagewise exposure is finished, a printing area 3 used for printing in a printing machine is formed on the exposed surface of the lithographic printing plate precursor 2. In the present embodiment, a plurality of print areas 3 are formed.
  • the print area 3 includes image information (characters to be printed, figures, etc.) including an exposed portion and a non-exposed portion.
  • the first information 5 including the exposed portion 5A and the non-exposed portion 5B is formed in the non-printing area 4 (see FIG. 4).
  • the first information 5 includes version information not used for printing.
  • the plate information may be expressed by characters whose contents can be recognized by a person, or may be expressed by a code whose contents can not be recognized by a person.
  • the first information 5 is formed in two places in the non-printing area 4, but it may be formed in at least one place.
  • FIG. 4 is a partially enlarged view of the first information 5.
  • the first information 5 includes, for example, “A” as a character.
  • the letter “A” is composed of the exposed portion 5A and the non-exposed portion 5B.
  • the non-printing area 4 of the lithographic printing plate precursor 2 is composed of only the non-exposure portion 5B.
  • imagewise exposure with the CTP device 20 in the form of “A” causes the exposed area in the form of “A” to develop color.
  • a color difference ⁇ E of 2 or more and 8 or less exists between the exposed portion 5A and the non-exposed portion 5B due to color development, and as a result, recognition as a character "A” becomes possible by utilizing the color difference ⁇ E.
  • the first information 5 is imaged by the imaging unit 40 shown in FIG.
  • the imaging unit 40 converts the first information 5 into first electronic information 50.
  • the first information 5 is converted into the first electronic information 50 by the imaging device of the imaging unit 40.
  • the first electronic information 50 is also imaging data of the first information 5.
  • the first electronic information 50 is transmitted to the control unit 70 via the first transmission unit 44.
  • the control unit 70 includes a processing unit 72 and a print control unit 74.
  • the control unit 70 controls the entire printing apparatus.
  • the first information 5 be irradiated with light having a wavelength of 620 nm or more and 750 nm or less, and the reflected light of the light be detected by the imaging unit 40.
  • the exposed portion 5A constituting the first information 5 has a peak emission wavelength in the range of 620 nm or more and 750 nm or less which is near infrared.
  • Light having a wavelength of 620 nm or more and 750 nm or less is reflected more than the non-exposed portion 5B by the exposed portion 5A of the first information 5, and the imaging portion 40 easily detects the difference between the exposed portion 5A and the non-exposed portion 5B. , Because the noise is reduced.
  • the first electronic information is converted into second electronic information.
  • the first electronic information 50 is input to the processing unit 72 of the control unit 70.
  • the processing unit 72 converts the first electronic information 50 into second electronic information 52.
  • the processing unit 72 performs binarization processing on the first electronic information 50 and converts the first electronic information 50 into second electronic information 52 which is a binarized image of the first electronic information 50.
  • the binarization processing means processing of converting imaging data having shades of gray into two gradations of white and black based on a certain threshold value.
  • FIG. 5 is a conceptual view of second electronic information 52 obtained by binarizing the first electronic information 50.
  • the first electronic information 50 has a density difference of color difference ⁇ E between the exposed portion 5A and the non-exposed portion 5B. Therefore, the first electronic information 50 to the second electronic information 52 are binarized based on a certain threshold, converting the exposed portion 5A of the first electronic information 50 into black and the non-exposed portion 5B into black. Converted to Although the binarization process is illustrated as a method of converting the first electronic information 50 into the second electronic information 52, the present invention is not limited to this.
  • the first information 5 has been described for the letter "A", but even if the first information 5 is expressed by a code instead of the letters, the first electronic information 50 is converted to the second electronic information 52. can do.
  • the setting of the threshold in the binarization process can be directly specified, or can be automatically obtained from a calculation formula or the like.
  • Step S4 In the printing step (step S4), the second information is printed on the lithographic printing plate precursor based on the second electronic information.
  • a control signal from the printing control unit 74 is transmitted through the second transmission unit 46, and the printing unit 60 This is executed by printing the two information on the lithographic printing plate precursor 2.
  • the first transmission unit 44 and the second transmission unit 46 may be wired or wireless as long as they can transmit electrical signals.
  • the second information includes version information (such as order reception number, JOBID (work identification number), customer information, color version name, screen type, sheet name, sheet size, etc.) that can be recognized by people.
  • version information such as order reception number, JOBID (work identification number), customer information, color version name, screen type, sheet name, sheet size, etc.
  • FIG. 6 is a plan view of the lithographic printing plate precursor after printing the second information.
  • the second information 6 is printed on the exposed surface of the lithographic printing plate precursor 2.
  • the second information 6 includes version information composed of characters that can be recognized by a person. Since the second information 6 is printed based on the second electronic information 52 after binarization, a person can easily recognize the plate information.
  • the second information 6 produced by printing is the exposed surface of the lithographic printing plate precursor 2 by at least one of dampening water and printing ink supplied to the printing machine. Removed from Therefore, the second information 6 can be printed so as to overlap the printing area 3 of the lithographic printing plate precursor 2. Further, the second information 6 can be displayed larger than the first information 5 so that a person can easily recognize the version information.
  • the ink on the surface of the lithographic printing plate precursor is removed with dampening water, and the ink in the overcoat layer of the lithographic printing plate precursor is removed together with the overcoat layer. It is estimated that the ink is removed by the printing ink.
  • the second electronic information 52 is information obtained by binarizing the first information 5, and the second electronic information 52 is the second.
  • the information is printed on the lithographic printing plate precursor 2 as the information 6.
  • the second electronic information 52 is converted to version information including character information that can be recognized by a person. Plate information after conversion is printed on the lithographic printing plate precursor 2 as second information 6.
  • the printing unit 60 is preferably, for example, a printing apparatus to which an inkjet recording method using an ink containing a dye is applied.
  • the inkjet recording method is a method of recording an image by discharging ink (ink droplets) to a target from a plurality of nozzles formed in a recording head.
  • a drop-on-demand method is preferable, and among these, a thermal method is preferable.
  • the drop-on-demand method means an ink jet recording method in which ink (ink droplets) is discharged only when it is necessary as a printing operation.
  • the thermal method means a method in which the ink is boiled by instantaneously raising the temperature by a heater, and the ink droplet is ejected from the nozzle by air bubbles.
  • the ink used to print plate information in the present embodiment is preferably an ink containing a dye as a colorant.
  • the solvent constituting the ink preferably contains pure water and an aqueous solvent.
  • pure water ion exchange water, distilled water, etc. are preferably used.
  • the aqueous solvent is suitably used to control the drying of the ink on the lithographic printing plate precursor for on-press development.
  • the ink is preferably contained in the range of 0.1 to 50% by mass.
  • the aqueous solvent it is preferable to use one or more of methyl alcohol, ethyl alcohol, isopropyl alcohol, t-butanol, glycerin, propylene glycol, ethylene glycol, polyethylene glycol, propylene glycol monomethyl ether, etc. It is more preferable to use species or more.
  • dyes contained in the ink commercially available dyes and known dyes described in documents such as "Dye Handbook” (edited by the Society of Synthetic Organic Chemistry, published in 1945) can be used. Specifically, dyes such as azo dyes, metal complex salt azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, cyanine dyes, squarylium dyes, pyrylium salts, metal thiolate complexes, etc. Can be mentioned.
  • azo dyes azo dyes, metal complex salt azo dyes, pyrazolone azo dyes, and carbonium dyes are preferable, and pyrazolone azo dyes and carbonium dyes are more preferable.
  • the diphenylmethane dye is preferably, for example, auramine.
  • the triphenylmethane dye is preferably at least one selected from the group consisting of diamino dyes, triamino dyes and oxyfexone dyes.
  • a diamino dye for example, malachite green (Malachite Green), brilliant green G (Brilliant Green G), setogrosin (Gy) (Setoglaucine (Gy)), rosulin blue 6G (IG) (Rhoduline Blue 6G (IG)), astra Zone Blue G (IG) (Astrazone Blue G (IG)), Fast Green FCF (Fast Green FCF), Brilliant Blue FCF (Brilliant Blue FCF), Light Green SF Yellowish (Light Green SF yellowish), Brilliant Milling Green G ( Brilliant Milling Green B), Patent Blue AF (Patent Blue AF), Wool Green S (Wool Green S), and Wool Green BS (Wool Green BS) are preferable.
  • a triamino dye for example, Para Rosaniline (Para Rosaniline), Methyl Violet (Methyl Violet), Crystal Violet (Crystal Violet), Victoria Blue B (Victoria Blue B), Soluble Blue (Souble Blue), Acid Violet (Acid Violet) is preferable.
  • chromoxan violet RS (Chromoxane Violet RS (IG)
  • chromoxan violet R (Gy)
  • chromoxan brilliant violet RE Chromoxane Brilliant Violet RE
  • chromomo It is preferable that it is xanthpure blue B (Chromoxane Pure Blue B) and chromoxane pure blue BX (Chromoxane Pure Blue BX).
  • the xanthene dye it is preferable to be a galein type and a rhodamine type.
  • a galain type it is preferable that they are gallein SW (Gallein SW) and Coeruelin S.
  • the rhodamines are preferably rhodamine B (Rodamine B), rhodamine SB (Rodamine SB), sulforhodamine B extra (Sulforhadamine B), and chromoxamine Brilliant Red BL.
  • the acridine dye is preferably acriflavine (Acriflavine), acridine orange NO (Axridine Orange NO), or phosphine C (Phosphine C).
  • the carbonium dyes are exemplified as described above, but are not limited thereto.
  • additives such as a water-soluble fixing agent, a mildewproofing agent, an anti-precipitation agent, a pH adjuster, an antifoaming agent, and a surfactant can be added as needed.
  • Example 1 Preparation of a lithographic printing plate precursor (1) for on-press development (for Examples 1 to 14) ⁇ Preparation of support>
  • an aluminum plate material JIS A 1050
  • it is degreased at 50 ° C for 30 seconds using a 10 mass% sodium aluminate aqueous solution, and then 0.3 mm
  • the surface of the aluminum plate was grained using three bundles of nylon brushes having a diameter of 50 mm and a pumice-water suspension with a median diameter of 25 ⁇ m (specific gravity: 1.1 g / cm 3 ) and thoroughly washed with water.
  • the aluminum plate was etched by immersing it in a 25% by mass aqueous solution of sodium hydroxide at 45 ° C. for 9 seconds, washed with water, and further immersed in a 20% by mass aqueous solution of nitric acid at 60 ° C. for 20 seconds and washed with water.
  • the etching amount of the grained surface was about 3 g / m 2 .
  • the electrolytic solution was a 1% by mass aqueous nitric acid solution (containing 0.5% by mass of aluminum ion), and the solution temperature was 50.degree.
  • the AC power supply waveform is electrochemically roughened with a carbon electrode as a counter electrode, using a trapezoidal rectangular wave AC with a time TP of 0.8 msec and a duty ratio of 1: 1 for the current value to reach a peak from zero Did. Ferrite was used for the auxiliary anode.
  • the current density was 30 A / dm 2 at the peak value of the current, and 5% of the current flowing from the power supply was diverted to the auxiliary anode.
  • the amount of electricity in nitric acid electrolysis was 175 C / dm 2 when the aluminum plate was an anode. After that, it was rinsed with a spray.
  • a 0.5% by mass aqueous hydrochloric acid solution (the aluminum aluminum plate contains 0.5% by mass of a conditional ion of 50 C / dm 2 of electric charge at the anode), an electrolytic solution with a solution temperature of 50 ° C., nitric acid
  • the electrochemical roughening treatment was performed in the same manner as the electrolysis, and then water washing by spraying was performed.
  • a direct current anodic oxide film of 2.5 g / m 2 is formed at a current density of 15 A / dm 2 with an aqueous solution of 15 mass% sulfuric acid (containing 0.5 mass% of aluminum ion) as an electrolytic solution on an aluminum plate,
  • the substrate was washed with water and dried to prepare a support A. It was 10 nm when the average pore diameter (surface average pore diameter) in the surface layer of the anodic oxide film was measured by the following method.
  • the support A is subjected to a silicate treatment at 60 ° C. for 10 seconds using a 2.5 mass% aqueous solution of No. 3 sodium silicate (JIS K 1408), and then washed with water Support B was produced.
  • the adhesion amount of Si was 10 mg / m 2 .
  • the center line average roughness (Ra) of the support was measured using a needle with a diameter of 2 ⁇ m and found to be 0.51 ⁇ m.
  • the undercoat layer coating solution (1) having the following composition was applied so that the coated amount after drying was 20 mg / m 2 to form an undercoat layer.
  • An image recording layer coating solution (1) of the following composition is bar-coated on the undercoat layer, and oven-dried at 100 ° C. for 60 seconds to form an image recording layer having a coating amount of 1.0 g / m 2 after drying. did.
  • the image recording layer coating solution (1) was prepared by mixing and stirring the following photosensitive solution and microgel solution immediately before coating.
  • Binder polymer (1) [the following structure] 0.240 g .
  • Polymerization initiator (1) [structure shown below] 0.245 g ⁇ Cyanine dye (X-1) [the following structure] 0.023 g ⁇ Borate compound [structure shown below] 0.010 g TPB: Sodium tetraphenylborate Sodium tetraphenylborate ⁇ Polymerizable monomer 0.192 g Tris (acryloyloxyethyl) isocyanurate (NK ester A-9300, Shin-Nakamura Chemical Co., Ltd.
  • Low molecular weight hydrophilic compound (1) [structure shown below] 0.050 g ⁇ Receptive agent 0.055 g Phosphonium compound (1) [structure shown below] ⁇ Receptive agent 0.018 g Benzyl-dimethyl-octyl ammonium ⁇ PF6 salt ⁇ sensitizing agent 0.035 g Ammonium group-containing polymer [structure below] [The following structure, reduced specific viscosity 44 ml / g] ⁇ Fluorinated surfactant (1) [structure shown below] 0.008 g ⁇ 2-butanone 1.091 g 1-methoxy-2-propanol 8.609 g ⁇ Micro gel solution> ⁇ Microgel (1) 2.640 g ⁇ Distilled water 2.425 g Binder polymer (1), cyanine dye (X-1), fluorosurfactant (1), low molecular weight hydrophilic compound
  • microgel (1) used for the said microgel liquid is shown below.
  • microgel (1) As an oil phase component, 10 g of trimethylolpropane and xylene diisocyanate adduct (Takenate D-110N, made by Mitsui Chemical Co., Ltd.), 3.15 g of pentaerythritol triacrylate (SR444, made by Nippon Kayaku Co., Ltd.) and alkylbenzene 0.1 g of a sulfonate (Pionin A-41C, manufactured by Takemoto Yushi Co., Ltd.) was dissolved in 17 g of ethyl acetate.
  • aqueous phase component 40 g of a 4% by mass aqueous solution of polyvinyl alcohol (PVA-205, manufactured by Kuraray Co., Ltd.) as an aqueous phase component was prepared.
  • the oil phase component and the water phase component were mixed and emulsified for 10 minutes at 12,000 rpm using a homogenizer.
  • the obtained emulsion was added to 25 g of distilled water and then stirred at room temperature for 30 minutes and then at 50 ° C. for 3 hours.
  • the solid concentration of the microgel solution thus obtained was diluted with distilled water to 15% by mass to prepare a microgel (1). It was 0.2 micrometer when the average particle diameter of microgel was measured by the light-scattering method.
  • a protective layer coating solution of the following composition is bar-coated on the above-mentioned image recording layer and dried by an oven at 120 ° C. for 60 seconds to form a protective layer having a dry coating amount of 0.15 g / m 2.
  • Lithographic printing plate precursors A for Examples 1 to 14 were prepared.
  • the preparation method of the inorganic stratiform compound dispersion liquid (1) used for the said protective layer coating liquid is shown below.
  • a lithographic printing plate precursor for on-press development (1) was manufactured by Fujifilm Co., Ltd.'s Luxel PLATESETTER T-6000 III equipped with an infrared semiconductor laser, with an outer surface drum rotational speed of 1000 rpm, a laser output of 70%, and a resolution of 2400 dpi. It exposed on condition. Printing was performed on a lithographic printing plate precursor (1) using an ink (1) of the following composition.
  • the obtained exposed original plate was mounted on a plate cylinder of a printing machine LITHRONE 26 manufactured by Komori Corporation without development processing.
  • Example 2 A lithographic printing plate precursor (2) to which printing was applied was produced in the same manner as in Example 1 except that an ink (2) having the following composition was used instead of the ink (1). Polyethylene glycol was added in order to prevent drying of the nozzle surface of the ink jet apparatus.
  • Example 3 A lithographic printing plate precursor (3) to which printing was applied was produced in the same manner as in Example 1 except that an ink (3) having the following composition was used instead of the ink (1).
  • Lithographic printing plate precursors (4) to (14) to which printing was applied were produced in the same manner as in Example 1 except that the above ink (1) colorant was changed to the colorant described in Table 1.
  • Ground dirt Background stains of the lithographic printing plate precursor (1) subjected to the printing described above were evaluated.
  • the ground stain refers to the ink deposited on the non-image area of the planographic printing plate precursor, which is the ink deposited on the lithographic printing plate precursor in order to prepare the second information. It is oleophilic due to ink remaining or having some effect on the non-image area.
  • the background dirt on the 500th printing start was evaluated according to the following level. The evaluation results are shown in Table 1. 5 to 3 are acceptable levels.
  • the blank stains with the 100th ink were evaluated according to the following levels.
  • the evaluation results are shown in Table 1. 5 to 3 are acceptable levels.
  • Examples 12 and 13 using the xanthene dye and Example 14 using the acridine dye were between 58 and 63 in the evaluation items of the on-press developability, and the background stain and the blank stain And 3 were evaluated for the evaluation items of leftover dirt.
  • Example 8 using a diphenylmethane dye and Examples 9 to 11 using an oxyfuxon dye are among 31 to 36 in the evaluation items of on-press developability, and are ground stains and blan stains. , And 4 evaluations for the evaluation items of the leftover dirt.
  • Examples 1 to 7 using the triamino dye are between 21 and 24 in the evaluation items of on-press developability, and for the evaluation items of background dirt, blan dirt, and left dirt. We received a rating of 5.
  • the present invention it is possible to print the second information (plate information) on the planographic printing plate precursor for on-press development, and the second information made of the ink containing the dye is used in the on-press development. It can be understood that good results can be obtained for the evaluation items of on-press developability, ground stain, blan stain, and left stain.

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Thermal Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Printing Plates And Materials Therefor (AREA)
  • Materials For Photolithography (AREA)

Abstract

L'invention concerne un procédé d'impression pour un cliché original de plaque d'impression à plat qui comprend : une étape de préparation d'un cliché original de plaque d'impression à plat pour un développement sur machine, le cliché original de plaque d'impression à plat comprenant une partie d'exposition basée sur une exposition sous forme d'image et une partie de non-exposition et présentant une différence de couleurs ∆E supérieure ou égale à deux et inférieure ou égale à huit, calculée selon la formule suivante, dans l'espace colorimétrique L*a*b entre la partie d'exposition et la partie de non-exposition ; une étape d'obtention d'image consistant à convertir des premières informations comprenant la partie d'exposition et la partie de non-exposition en premières informations électroniques ; une étape de traitement consistant à convertir les premières informations électroniques en secondes informations électroniques ; et une étape d'impression consistant à imprimer les secondes informations sur le cliché original de plaque d'impression à plat sur la base des secondes informations électroniques. (Formule) : ∆E = ((L2* - L1*)2 + (a2* - a1*)2 + (b1* - b2*)2)1/2 où L1*, a1* et b1* représentent les valeurs de la partie d'exposition, et L2*, a2*, et b2* représentent les valeurs de la partie de non-exposition.
PCT/JP2017/047234 2017-12-28 2017-12-28 Procédé d'impression pour cliché original de plaque d'impression à plat et appareil d'impression pour cliché original de plaque d'impression à plat WO2019130547A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002287322A (ja) * 2001-03-28 2002-10-03 Dainippon Screen Mfg Co Ltd 検版方法および検版装置ならびに製版装置
JP2006285189A (ja) * 2004-09-21 2006-10-19 Fuji Photo Film Co Ltd 印刷版の作製方法および装置
JP2007086564A (ja) * 2005-09-26 2007-04-05 Ryobi Ltd 印刷版管理方法、ｃｔｐ装置および印刷機
WO2015122513A1 (fr) * 2014-02-17 2015-08-20 富士フイルム株式会社 Procédé de détection de marque de référence pour planche d'impression à plat, procédé de traitement pour planche d'impression à plat et procédé d'impression
US20160067953A1 (en) * 2014-09-10 2016-03-10 Gary Ganghui Teng Lithographic printing press and method for on-press imaging laser sensitive lithographic plate

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002287322A (ja) * 2001-03-28 2002-10-03 Dainippon Screen Mfg Co Ltd 検版方法および検版装置ならびに製版装置
JP2006285189A (ja) * 2004-09-21 2006-10-19 Fuji Photo Film Co Ltd 印刷版の作製方法および装置
JP2007086564A (ja) * 2005-09-26 2007-04-05 Ryobi Ltd 印刷版管理方法、ｃｔｐ装置および印刷機
WO2015122513A1 (fr) * 2014-02-17 2015-08-20 富士フイルム株式会社 Procédé de détection de marque de référence pour planche d'impression à plat, procédé de traitement pour planche d'impression à plat et procédé d'impression
US20160067953A1 (en) * 2014-09-10 2016-03-10 Gary Ganghui Teng Lithographic printing press and method for on-press imaging laser sensitive lithographic plate

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