WO2015129504A1 - 機上現像型平版印刷版原版の処理方法及び印刷方法 - Google Patents
機上現像型平版印刷版原版の処理方法及び印刷方法 Download PDFInfo
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- WO2015129504A1 WO2015129504A1 PCT/JP2015/054145 JP2015054145W WO2015129504A1 WO 2015129504 A1 WO2015129504 A1 WO 2015129504A1 JP 2015054145 W JP2015054145 W JP 2015054145W WO 2015129504 A1 WO2015129504 A1 WO 2015129504A1
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- recording layer
- image recording
- printing plate
- lithographic printing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C1/00—Forme preparation
- B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
- B41C1/1041—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by modification of the lithographic properties without removal or addition of material, e.g. by the mere generation of a lithographic pattern
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/38—Treatment before imagewise removal, e.g. prebaking
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C1/00—Forme preparation
- B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
- B41C1/1075—Mechanical aspects of on-press plate preparation
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- 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
- B41N3/00—Preparing for use and conserving printing surfaces
- B41N3/08—Damping; Neutralising or similar differentiation treatments for lithographic printing formes; Gumming or finishing solutions, fountain solutions, correction or deletion fluids, or on-press development
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/30—Imagewise removal using liquid means
- G03F7/3035—Imagewise removal using liquid means from printing plates fixed on a cylinder or on a curved surface; from printing cylinders
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C1/00—Forme preparation
- B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
- 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
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- 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
- B41C2210/04—Negative working, i.e. the non-exposed (non-imaged) areas are removed
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- 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
- B41C2210/08—Developable by water or the fountain solution
Definitions
- the present invention relates to a processing method and a printing method for an on-press development type lithographic printing plate precursor.
- the present invention relates to a processing method and a printing method for an on-press development type lithographic printing plate precursor that provides a lithographic printing plate that prevents edge smearing and has a wide water width during printing.
- lithographic printing plate precursors due to growing interest in the global environment, another issue related to lithographic printing plate precursors is the close-up of environmental issues related to waste liquids associated with wet processing such as development processing. In connection with this, simplification of development processing or no processing is directed.
- a method called “on-press development” has been proposed. In other words, after the lithographic printing plate precursor is exposed, the conventional development processing is not performed, and the lithographic printing plate precursor is mounted on a printing machine as it is, and unnecessary portions of the image recording layer are removed at the initial stage of the normal printing process.
- edge of the printing plate when printing on paper smaller than the printing plate size as in a normal sheet-fed printing press, the edge of the printing plate is located outside the paper surface. Does not affect print quality. However, when printing on roll paper continuously using a rotary press such as newspaper printing, the edge of the printing plate is in the roll paper surface, so the ink attached to the edge is transferred to the paper. As a result, linear stains (edge stains) are generated, and the commercial value of the printed matter is significantly impaired.
- the edge contamination is improved to some extent according to the above prior art, the contamination of the unexposed portion increases mainly in the region near the boundary between the treatment liquid application portion and the non-application portion (hereinafter also referred to as the edge vicinity region). Turned out to be. It has also been found that edge smears are not sufficiently eliminated when the amount of dampening water is reduced during printing. This means that the water width during printing is narrow.
- the water width refers to the width from the upper limit to the lower limit of the amount of dampening water for maintaining printability, and a wide water width is strongly required for stable printing.
- An object of the present invention is to provide an on-press development type lithographic printing plate precursor that does not cause edge smearing, has no unexposed part smear in the vicinity of the edge part, and gives a lithographic printing plate having a wide water width during printing against edge smearing. It is to provide a processing method and a printing method.
- the object of the present invention is achieved by the following method.
- an on-press development type lithographic printing plate precursor that gives a lithographic printing plate that does not cause edge smearing, has no unexposed part in the vicinity of the edge part, and has a wide water width at the time of printing against edge smearing.
- a processing method and a printing method can be provided.
- the processing method of the on-press development type lithographic printing plate precursor according to the present invention comprises the following steps: lithographic printing after the on-press development type lithographic printing plate precursor having an image recording layer on the support is subjected to image exposure and then mounted on the printing press.
- This is a processing method in which a treatment liquid containing a hydrophilizing agent is applied to an area within 1 cm from the edge of the plate surface of the plate precursor, and the coating is performed so that the coating means does not contact the plate surface.
- the processing method of the present invention is characterized in that the coating means does not come into contact with the plate surface when the treatment liquid containing a hydrophilizing agent is applied to the end region of the plate surface of the lithographic printing plate precursor.
- the coating means comes into contact with the plate surface, a physical force is applied to the image recording layer of the lithographic printing plate precursor, the image recording layer is damaged and film is removed. Such a problem does not occur in the processing method of the present invention. Furthermore, according to the treatment method of the present invention, the amount of dampening water at the time of printing is reduced by applying the application means so as not to contact the plate surface as compared with the case where the application means is applied in contact with the plate surface. Even in this case, it was found that an unexpectedly excellent effect of suppressing the occurrence of edge contamination was observed. First, a treatment liquid containing a hydrophilizing agent used in the treatment method according to the present invention will be described.
- the treatment liquid containing the hydrophilizing agent used in the treatment method of the present invention may be an aqueous solution or a treatment liquid (emulsification type treatment liquid) emulsified with an oil phase component and an aqueous phase component. It is preferable that
- the hydrophilizing agent contained in the treatment liquid is preferably at least one selected from a phosphoric acid compound, a phosphonic acid compound, an anionic surfactant, and a nonionic surfactant.
- a phosphoric acid compound and a phosphonic acid compound are preferable. More preferably, the hydrophilizing agent is at least one selected from a phosphoric acid compound and a phosphonic acid compound, and at least one selected from an anionic surfactant and a nonionic surfactant.
- phosphoric acid or a salt thereof is preferably used.
- a combination of an acid and a salt such as phosphoric acid / ammonium phosphate, phosphoric acid / sodium phosphate, and metaphosphoric acid / ammonium phosphate can be preferably used.
- phosphonic acid compound used as the hydrophilizing agent phosphonic acid, a salt thereof, and an ester thereof are preferably used.
- Alkyl phosphonate monoesters such as dodecylphosphonic acid, octadecylphosphonic acid, 2-hydroxyethylphosphonic acid and sodium or potassium salts thereof
- alkyl esters and sodium or potassium salts thereof alkylene diphosphonic acids such as methylene diphosphonic acid and ethylene diphosphonic acid, and sodium or potassium salts thereof.
- the content of the phosphoric acid compound or phosphonic acid compound in the treatment liquid used in the present invention is preferably 0.5 to 10.0% by mass, more preferably 0.5 to 5% by mass, based on the total mass of the treatment liquid. preferable. Within this range, it is more excellent in terms of edge contamination and suppression of crystal precipitation after coating.
- Anionic surfactants used as hydrophilizing agents include fatty acid salts, abietic acid salts, hydroxyalkane sulfonic acid salts, alkane sulfonic acid salts, dialkyl sulfosuccinic acid salts, benzene sulfonic acid salts, linear alkyl benzene sulfonic acid salts, branched Chain alkylbenzene sulfonates, naphthalene sulfonates, alkyl naphthalene sulfonates, alkylphenoxy polyoxyethylene propyl sulfonates, polyoxyethylene aryl ether sulfate esters, polyoxyethylene alkyl sulfophenyl ether salts, N-methyl-N -Oleyl taurine sodium, N-alkylsulfosuccinic acid monoamide disodium salt, petroleum sulfonates, sulfated
- dialkyl sulfosuccinates alkyl sulfates, polyoxyethylene aryl ether sulfates and alkyl naphthalene sulfonates are preferably used.
- anionic surfactants represented by the following general formula (IA) or general formula (IB) can be preferably mentioned.
- R 1 represents a linear or branched alkyl group having 1 to 20 carbon atoms, p represents 0, 1 or 2, and Ar 1 represents 6 to 10 carbon atoms.
- M 1 + represents Na + , K + , Li + or NH 4 + ;
- R 2 represents a linear or branched alkyl group having 1 to 20 carbon atoms, m represents 0, 1 or 2, and Ar 2 represents 6 to 10 carbon atoms.
- Y represents a single bond or an alkylene group having 1 to 10 carbon atoms
- R 3 represents a linear or branched alkylene group having 1 to 5 carbon atoms
- n represents an integer of 1 to 100
- M 2 + represents Na + , K + , Li + or NH 4 + .
- m 2
- n 2 or more
- a plurality of R 3 may be the same or different from each other.
- R 1 and R 2 include CH 3 , C 2 H 5 , C 3 H 7 or C 4 H 9 .
- Preferred examples of R 3 are each -CH 2 -, - CH 2 CH 2 -, - CH 2 CH 2 CH 2 -, - CH 2 CH (CH 3) - can be mentioned, -CH As a more preferable example 2 CH 2 —.
- p and m are preferably 0 or 1, and p is particularly preferably 0.
- Y is preferably a single bond.
- n is preferably an integer of 1 to 20.
- anionic surfactant represented by formula (IA) or formula (IB) are shown below.
- Nonionic surfactants used as hydrophilizing agents include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkyl esters, glycerin fatty acid partial esters, sorbitan fatty acid partial esters, pentaerythritol Fatty acid partial esters, propylene glycol mono fatty acid esters, sucrose fatty acid partial esters, polyoxyethylene sorbitan fatty acid partial esters, polyoxyethylene sorbitol fatty acid partial esters, polyethylene glycol fatty acid esters, polyglycerin fatty acid partial esters, Polyoxyethylene glycerin fatty acid partial esters, fatty acid diethanolamides, N, N-bis-2-hydroxyalkylamines, polyoxyethylene amines Kiruamin acids, triethanolamine fatty acid esters, trialkylamine oxides, polyoxyethylene - polyoxypropylene block copolymers can be mentioned. Note that the fluorine-based
- nonionic surfactants polyoxyethylene aryl ethers, polyoxyethylene-polyoxypropylene block copolymers and the like are preferably used.
- a nonionic surfactant represented by the following general formula (II-A) can be preferably exemplified.
- R 4 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms
- s represents 0, 1 or 2
- Ar 3 represents an aryl group having 6 to 10 carbon atoms.
- T and u each represent an integer of 0 to 100, and both t and u are never 0.
- a plurality of R 4 may be the same as or different from each other.
- the compound represented by the general formula (II-A) is polyoxyethylene phenyl ether, polyoxyethylene methyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene naphthyl ether, polyoxyethylene.
- Examples include methyl naphthyl ether, polyoxyethylene octyl naphthyl ether, and polyoxyethylene nonyl naphthyl ether.
- the number of repeating units (t) of the polyoxyethylene chain is preferably 2 to 50, more preferably 4 to 30, and the number of repeating units of the polyoxypropylene chain.
- (U) is preferably 0 to 10, more preferably 0 to 5.
- the polyoxyethylene part and the polyoxypropylene part may be present randomly or as a block.
- nonionic surfactants are shown.
- the oxyethylene repeating unit and the oxypropylene repeating unit in the exemplified compound “Y-5” shown below can take either random bond or block connection.
- Two or more of the above surfactants can be used in combination.
- a combination of two or more different anionic surfactants, a combination of two or more different nonionic surfactants, and a combination of an anionic surfactant and a nonionic surfactant may be mentioned.
- the content of the anionic surfactant or the nonionic surfactant in the treatment liquid used in the present invention is preferably 0.01 to 20% by mass, preferably 0.1 to 15% by mass based on the total mass of the treatment liquid. % Is more preferable.
- the treatment liquid containing the hydrophilic agent by using the treatment liquid containing the hydrophilic agent, edge stains are not generated, there is no stain on unexposed portions in the vicinity of the edge portion, and the edge.
- the treatment liquid further contains a water-soluble resin, an organic solvent, a plasticizer, and other additives as necessary. You may do it.
- the water-soluble resin can be contained for the purpose of sustaining the effect of preventing edge stains by adjusting the viscosity and forming a hydrophilic protective film.
- water-soluble resins include water-soluble resins classified as polysaccharides, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide and copolymers thereof, vinyl methyl ether / maleic anhydride copolymers, vinyl acetate / maleic anhydride copolymers. And styrene / maleic anhydride copolymer.
- polysaccharides examples include starch derivatives (eg, dextrin, enzymatically degraded dextrin, hydroxypropylated starch, carboxymethylated starch, phosphate esterified starch, polyoxyalkylene grafted starch, cyclodextrin), celluloses (eg, carboxymethylcellulose) Carboxyethylcellulose, methylcellulose, hydroxypropylcellulose, methylpropylcellulose), carrageenan, alginic acid, guar gum, locust bean gum, xanthan gum, gum arabic, soybean polysaccharide and the like.
- starch derivatives such as dextrin and polyoxyalkylene grafted starch, gum arabic, carboxymethyl cellulose, soybean polysaccharide and the like are preferably used.
- the content of the water-soluble resin is preferably 0.5 to 30% by mass, more preferably 1 to 10% by mass, based on the total mass of the treatment liquid. Within this range, good coating properties of the treatment liquid and durability of the effect of preventing edge contamination due to the formation of a hydrophilic protective film can be obtained.
- Organic solvent can be contained for the purpose of promoting the hydrophilic property, the solubility adjustment of the water-soluble resin, and the swelling of the image recording layer.
- organic solvent include alcohol solvents, ketone solvents, ester solvents, amide solvents, hydrocarbon solvents, and the like.
- organic solvents alcohol solvents and hydrocarbon solvents are preferably used.
- the alcohol solvent may be a monohydric alcohol or a polyhydric alcohol.
- Monohydric alcohols include methyl alcohol, n-propyl alcohol, iso-propyl alcohol, n-butyl alcohol, tert-butyl alcohol, n-amyl alcohol, diacetone alcohol, 1-methoxy-2-propanol, furfuryl alcohol 2-octanol, 2-ethylhexanol, nonanol, n-decanol, undecanol, n-dodecanol, trimethylnonyl alcohol, benzyl alcohol, phenethyl alcohol, ethylene glycol monoisoamyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, And ethylene glycol monohexyl ether.
- polyhydric alcohol examples include ethylene glycol, propylene glycol, triethylene glycol, butylene glycol, hexylene glycol, diethylene glycol, dipropylene glycol, and glycerin.
- hydrocarbon solvents examples include aromatic or aliphatic compounds (mineral spirits), squalane and the like of petroleum fractions.
- the content of the organic solvent is preferably 0.5 to 10% by mass, more preferably 1 to 5% by mass, based on the total mass of the treatment liquid. Within this range, the control of the application width of the treatment liquid and the permeability to the image recording layer are excellent.
- Plasticizers include dibutyl phthalate, diheptyl phthalate, di-n-octyl phthalate, di (2-ethylhexyl) phthalate, dinonyl phthalate, didecyl phthalate, dilauryl phthalate, butyl benzyl phthalate, and the like, dioctyl Aliphatic dibasic acid esters such as adipate, butyl glycol adipate, dioctyl azelate, dibutyl sebacate, di (2-ethylhexyl) sebacate, dioctyl sebacate, epoxidized triglycerides such as epoxidized soybean oil, tricresyl phosphate Plasticizers having a freezing point of 15 ° C. or less, such as phosphate esters such as a shade, trioctyl phosphate, tristrol ethyl phosphate, and
- the content of the plasticizer is preferably 0.5 to 10% by mass, more preferably 1 to 5% by mass, based on the total mass of the treatment liquid.
- the treatment liquid containing a hydrophilizing agent may contain inorganic salts such as nitrates and sulfates, preservatives, antifoaming agents, and the like.
- inorganic salts include magnesium nitrate, sodium nitrate, potassium nitrate, ammonium nitrate, sodium sulfate, potassium sulfate, ammonium sulfate, sodium hydrogen sulfate, nickel sulfate and the like.
- Preservatives include phenol or derivatives thereof, formalin, imidazole derivatives, sodium dehydroacetate, 4-isothiazolin-3-one derivatives, benzisothiazolin-3-one, benztriazole derivatives, amiding anidine derivatives, quaternary ammonium salts, pyridine, Derivatives such as quinoline and guanidine, diazine, triazole derivatives, oxazole, oxazine derivatives, nitrobromoalcohol-based 2-bromo-2-nitropropane-1,3diol, 1,1-dibromo-1-nitro-2-ethanol, Examples include 1,1-dibromo-1-nitro-2-propanol.
- the antifoaming agent a general silicon-based self-emulsifying type, emulsifying type, or nonionic surfactant having an HLB of 5 or less can be used.
- the treatment liquid containing a hydrophilizing agent may contain a cationic surfactant or an amphoteric surfactant.
- the cationic surfactant include alkylamine salts, quaternary ammonium salts, polyoxyalkylamine salts, polyethylene polyamine derivatives, and the like.
- amphoteric surfactants include carboxybetaines, aminocarboxylic acids, sulfobetaines, aminosulfuric esters, imidazolines, and the like.
- the treatment liquid containing the hydrophilizing agent can be prepared according to a conventional method.
- the treatment liquid is an aqueous solution, it is prepared by dissolving a hydrophilizing agent and other components as necessary in water (distilled water, ion exchange water, demineralized water, etc.). Even in the case of an emulsified processing solution, it can be prepared according to a conventional method.
- the emulsification dispersion at the time of preparing the treatment liquid is, for example, preparing an aqueous phase containing a hydrophilizing agent at a temperature of 40 ° C. ⁇ 5 ° C.
- the treatment liquid containing the hydrophilizing agent is first prepared in a concentrated form and may be appropriately diluted at the time of use.
- the coating means does not contact the plate surface with the processing liquid containing the hydrophilizing agent in an area within 1 cm from the edge of the plate surface of the on-press development type lithographic printing plate precursor subjected to image exposure.
- the plate surface of the lithographic printing plate precursor means the surface of the lithographic printing plate precursor on the side having the image recording layer, and is usually the image recording layer surface or the protective layer surface provided on the image recording layer.
- the end portion refers to an edge portion formed by a step of cutting into a sheet shape in the process of producing a lithographic printing plate precursor.
- the treatment liquid containing the hydrophilizing agent is applied to an area within 1 cm from the end. In the area within 1 cm from the end, there is usually no image.
- the treatment liquid is preferably applied to a region within 0.5 cm from the end, and particularly preferably within a region within 0.3 cm from the end.
- the coating amount of the treatment liquid to be applied in the end region, as a solid after drying is preferably 0.05 ⁇ 3g / m 2, more preferably 0.1 ⁇ 2g / m 2. This range is preferable from the viewpoints of prevention of adhesion between lithographic printing plate precursors due to stickiness of the coated portion and influence on on-press developability.
- the treatment method according to the present invention is characterized in that a treatment liquid containing a hydrophilizing agent is applied so that the application means does not contact the plate surface. Applying the treatment liquid so that the application means does not contact the plate surface, the application means contacts the plate surface of the lithographic printing plate precursor so that physical force is applied to the plate surface and the plate surface is not damaged. That is, the application means used includes various non-contact application means.
- a liquid fixed quantity discharge device is preferably used as the non-contact type application means.
- the liquid fixed quantity discharge device is a device that can supply a fixed amount of liquid with high accuracy, and examples thereof include a spray method, an ink jet method, a dispenser method, a die coating method, and the like.
- a dispenser type application means is preferable.
- the application using a cloth containing a treatment liquid, a Morton roll, or the like is performed because the application means contacts the plate surface of the lithographic printing plate precursor. It does not correspond to apply
- a charge control method As the ink jet method, a charge control method, a pressure vibration method, an electromechanical conversion method, an electrothermal conversion method, and an electrostatic suction method can be used.
- an air compression method As the dispenser method, an air compression method, a valve opening / closing method, a piston method, a tube method, or a screw discharge method can be used.
- the processing liquid may be applied to the edge region of the sheet-like lithographic printing plate precursor one by one, or after exposure,
- the treatment liquid may be applied to the end region of the lithographic printing plate precursor stacked in a bundle state.
- the mode of coating one sheet at a time is preferable from the viewpoint of preventing adhesion between lithographic printing plate precursors due to stickiness of the coated portion.
- the treatment liquid contains a plurality of components
- a method of applying the treatment liquid containing the surfactant and other components at a time is preferable. It is also possible to use a sequential coating method in which a solution containing other components is applied after a solution containing an active agent is applied. Each solution can be applied multiple times. Moreover, you may give a drying process after an application
- the image recording layer in the end region may be removed by irradiating with a high-power carbon dioxide laser or the like or by cutting before applying the treatment liquid to the lithographic printing plate precursor after image exposure.
- the drying step can be performed using an oven or by blowing dry air. A combination of these may also be used.
- the drying temperature is preferably 50 to 250 ° C, more preferably 60 to 160 ° C.
- the drying time is preferably 3 to 180 seconds, and more preferably 5 to 90 seconds.
- the drying step is performed by appropriately combining the drying temperature and the drying time within a range that does not adversely affect the performance of the lithographic printing plate precursor.
- the on-press development type lithographic printing plate precursor (hereinafter sometimes simply referred to as “lithographic printing plate precursor”) used in the processing method of the present invention has an image recording layer on a support.
- the lithographic printing plate precursor has 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, if necessary. May be.
- the image recording layer of the lithographic printing plate precursor is an image recording layer whose non-image area is removed by at least one of neutral to alkaline dampening water and printing ink on a printing press.
- the image recording layer is an image recording layer (hereinafter also referred to as image recording layer A) containing an infrared absorber, a polymerization initiator, a polymerizable compound, and a binder polymer.
- the image recording layer contains an infrared absorber, a polymerization initiator, a polymerizable compound and a polymer compound in the form of fine particles (hereinafter also referred to as image recording layer B). It is.
- the image recording layer is an image recording layer (hereinafter also referred to as image recording layer C) containing an infrared absorber and a thermoplastic fine particle polymer.
- the image recording layer A contains an infrared absorber, a polymerization initiator, a polymerizable compound, and a binder polymer.
- an infrared absorber a polymerization initiator
- a polymerizable compound a polymerizable compound
- a binder polymer a binder polymer
- the infrared absorber has a function of converting absorbed infrared light into heat and a function of being excited by infrared light and transferring electrons and / or energy to a polymerization initiator described later.
- the infrared absorber used in the present invention is preferably a dye or pigment having an absorption maximum at a wavelength of 760 to 1200 nm, more preferably a dye.
- dyes such as 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 salts, metal thiolate complexes Is mentioned.
- cyanine dyes particularly preferred among these dyes are cyanine dyes, squarylium dyes, pyrylium salts, nickel thiolate complexes, and indolenine cyanine dyes. Further, cyanine dyes and indolenine cyanine dyes are preferred, and particularly preferred examples include cyanine dyes represented by the following general formula (a).
- 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 or different and each may have a substituent, an aryl group having 6 to 10 carbon atoms, an alkyl group having 1 to 8 carbon atoms, a hydrogen atom R 9 and R 10 may be bonded to each other to form a ring. Of these, a phenyl group is preferred (—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.
- a hetero atom here shows N, S, O, a halogen atom, and Se.
- Xa - has Za described later - is defined as for, Ra represents a hydrogen atom, an alkyl group, an aryl group, a substituted or unsubstituted amino group, substituted or unsubstituted amino group and a halogen atom.
- R 1 and R 2 each independently represents a hydrocarbon group having 1 to 12 carbon atoms.
- R 1 and R 2 are preferably hydrocarbon groups having 2 or more carbon atoms.
- R 1 and R 2 may be connected to each other to form a ring, and when a ring is formed, it is particularly preferable to form a 5-membered ring or a 6-membered ring.
- Ar 1 and Ar 2 may be the same or different and each represents an aryl group which may have a substituent.
- Preferred aryl groups include a benzene ring and a naphthalene ring.
- a C12 or less hydrocarbon group, a halogen atom, and a C12 or less alkoxy group are mentioned.
- Y 1 and Y 2 may be the same or different and each represents a sulfur atom or a dialkylmethylene group having 12 or less carbon atoms.
- R 3 and R 4 may be the same or different and each represents a hydrocarbon group having 20 or less carbon atoms which may have a substituent.
- Preferred substituents include alkoxy groups having 12 or less carbon atoms, carboxy groups, and sulfo groups.
- R 5 , R 6 , R 7 and R 8 may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 12 or less carbon atoms. From the availability of raw materials, a hydrogen atom is preferred.
- Za ⁇ represents a counter anion. However, Za ⁇ is not necessary when the cyanine dye represented by formula (a) has an anionic substituent in its structure and neutralization of charge is not necessary.
- Preferred Za ⁇ is a halide ion, a perchlorate ion, a tetrafluoroborate ion, a hexafluorophosphate ion, and a sulfonate ion, particularly preferably a perchlorate ion, in view of the storage stability of the image recording layer coating solution.
- Hexafluorophosphate ions, and aryl sulfonate ions are examples of the storage stability of the image recording layer coating solution.
- cyanine dye represented by formula (a) that can be preferably used include compounds described in paragraph numbers [0017] to [0019] of JP-A No. 2001-133969, JP-A No. 2002-023360.
- Paragraph Nos. [0016] to [0021] and compounds described in Paragraph Nos. [0012] to [0037] in JP-A No. 2002-040638, preferably Paragraph Nos. [0034] to [0034] in JP-A No. 2002-278057.
- pigments examples include commercially available pigment and color index (CI) manuals, “Latest Pigment Handbook” (edited by the Japan Pigment Technology Association, published in 1977), “Latest Pigment Applied Technology” (published by CMC, published in 1986), “Printing” The pigments described in “Ink Technology” (CMC Publishing, 1984) can be used.
- CI pigment and color index
- the particle diameter of the pigment is preferably 0.01 to 1 ⁇ m, more preferably 0.01 to 0.5 ⁇ m.
- a known dispersion technique used for ink production or toner production can be used. Details are described in “Latest Pigment Applied Technology” (CMC Publishing, 1986).
- An infrared absorber may use only 1 type and may use 2 or more types together.
- the content of the infrared absorber is preferably 0.05 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, and 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. Part by mass.
- the polymerization initiator is a compound that initiates and accelerates the polymerization of the polymerizable compound.
- a known thermal polymerization initiator, a compound having a bond with a small bond dissociation energy, a photopolymerization initiator, or the like can be used.
- examples of the polymerization initiator include (a) an organic halide, (b) a carbonyl compound, (c) an azo compound, (d) an organic peroxide, (e) a metallocene compound, and (f) an azide.
- azo compound for example, an azo compound described in JP-A-8-108621 can be used.
- organic peroxide for example, a compound described in paragraph [0025] of JP-A-2008-195018 is preferable.
- Examples of the azide compound include 2,6-bis (4-azidobenzylidene) -4-methylcyclohexanone.
- Examples of the hexaarylbiimidazole compound for example, the compound described in paragraph [0027] of JP-A-2008-195018 is preferable.
- organic borate compound for example, compounds described in paragraph No. [0028] of JP-A-2008-195018 are preferable.
- Examples of the disulfone compound include compounds described in JP-A No. 61-166544.
- onium salt compounds examples include S.I. I. Schlesinger, Photogr. Sci. Eng. , 18, 387 (1974), T.A. S. Bal et al, Polymer, 21, 423 (1980), diazonium salts described in JP-A-5-158230, ammonium described in US Pat. No. 4,069,055, JP-A-4-365049, etc. Salt, phosphonium salts described in U.S. Pat. Nos. 4,069,055 and 4,069,056, EP 104,143, U.S. Patent Application Publication No. 2008/0311520 JP-A-2-150848, JP-A-2008-195018, or J.P. V.
- preferred compounds include onium salts, especially iodonium salts and sulfonium salts.
- iodonium salts include diphenyl iodonium salts, particularly diphenyl iodonium salts substituted with an electron donating group such as an alkyl group or an alkoxyl group, and more preferably asymmetric diphenyl iodonium salts.
- diphenyliodonium hexafluorophosphate
- 4-methoxyphenyl-4- (2-methylpropyl) phenyliodonium hexafluorophosphate
- 4- (2-methylpropyl) phenyl-p-tolyliodonium hexa Fluorophosphate
- 4-hexyloxyphenyl-2,4,6-trimethoxyphenyliodonium hexafluorophosphate
- 4-hexyloxyphenyl-2,4-diethoxyphenyliodonium tetrafluoroborate
- 4-octyloxy Phenyl-2,4,6-trimethoxyphenyliodonium 1-perfluorobutanesulfonate
- 4-octyloxyphenyl-2,4,6-trimethoxyphenyliodonium hexafluorophosphate, bis ( -t- butylphenyl) iodonium
- organic borate compounds are also preferably used.
- the organic borate compound 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 -Butylphenyl) borate salt, ethyltriphenylborate salt, butyltriphenylborate salt and the like.
- a tetraphenylborate salt is preferable.
- 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 stain resistance of the non-image area 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 terminal ethylenically unsaturated bond, preferably two or more. These have chemical forms such as monomers, prepolymers, ie dimers, trimers and oligomers, or mixtures thereof.
- Examples of monomers include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters and amides thereof, preferably unsaturated carboxylic acids.
- An ester of an acid and a polyhydric alcohol compound and an amide of an unsaturated carboxylic acid and a polyvalent amine compound are used.
- an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxy group, an amino group or a mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and a monofunctional or polyfunctional compound.
- a dehydration condensation reaction product with a functional carboxylic acid is also preferably used.
- a substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable.
- monomers of esters of polyhydric alcohol compounds and unsaturated carboxylic acids include acrylic acid esters such as ethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, Examples include trimethylolpropane triacrylate, hexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol tetraacrylate, sorbitol triacrylate, isocyanuric acid ethylene oxide (EO) -modified triacrylate, and polyester acrylate oligomer.
- acrylic acid esters such as ethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate
- Examples include trimethylolpropane triacrylate, hexanediol diacrylate, tetraethylene glycol diacrylate, pentaery
- Methacrylic acid esters include tetramethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, pentaerythritol trimethacrylate, bis [p- (3-methacryloxy-2-hydroxypropoxy) phenyl ] Dimethylmethane, bis- [p- (methacryloxyethoxy) phenyl] dimethylmethane, and the like.
- amide monomers of polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis-methacrylic.
- examples include amide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, and xylylene bismethacrylamide.
- urethane-based addition polymerizable compounds produced by an addition reaction of isocyanate and hydroxy group are also suitable. Specific examples thereof include, for example, one molecule described in JP-B-48-41708.
- a vinyl containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxy group represented by the following general formula (b) to a polyisocyanate compound having two or more isocyanate groups.
- a urethane compound etc. are mentioned.
- CH 2 C (R 4) COOCH 2 CH (R 5) OH (b) (However, R 4 and R 5 represent H or CH 3. )
- urethanes as described in JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, JP-A-2003-344997, JP-A-2006-65210 are disclosed.
- Acrylates, JP-B 58-49860, JP-B 56-17654, JP-B 62-39417, JP-B 62-39418, JP-A 2000-250211, JP-A 2007-94138 Urethane compounds having an ethylene oxide-based skeleton described in the publication, and urethane compounds having a hydrophilic group described in US Pat. No. 7,153,632, JP-T 8-505958, JP-A 2007-293221, and JP-A 2007-293223. Are also suitable.
- tris (acryloyloxyethyl) isocyanurate, bis (acryloyloxyethyl) hydroxyethyl isocyanurate, etc. are excellent in the balance between the hydrophilicity involved in on-press developability and the polymerization ability involved in printing durability.
- Isocyanuric acid ethylene oxide modified acrylates are particularly preferred.
- the polymerizable compound is preferably used in the range of 5 to 75% by mass, more preferably 10 to 70% by mass, and particularly preferably 15 to 60% by mass with respect to 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.
- a conventionally well-known thing can be used for a binder polymer,
- the polymer which has film property is preferable.
- acrylic resins, polyvinyl acetal resins, polyurethane resins and the like are preferable.
- the main chain or the side chain preferably the side chain, has a crosslinkable functional group for improving the film strength of the image area. Things. Crosslinking is formed between the polymer molecules by the crosslinkable group, and curing is accelerated.
- the crosslinkable functional group is preferably an ethylenically unsaturated group such as a (meth) acryl group, vinyl group, allyl group, or styryl group, or an epoxy group.
- the crosslinkable functional group is introduced into the polymer by polymer reaction or copolymerization. can do. For example, a reaction between an acrylic polymer or polyurethane having a carboxy group in the side chain and polyurethane and glycidyl methacrylate, or a reaction between a polymer having an epoxy group and 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.
- hydrophilic group examples include a hydroxy group, a carboxy group, an alkylene oxide structure, an amino group, an ammonium group, an amide group, a sulfo group, and a phosphoric acid group.
- an alkylene oxide unit having 2 or 3 carbon atoms An alkylene oxide structure having 1 to 9 is preferred.
- the hydrophilic group can be imparted to the binder polymer by, for example, copolymerizing a monomer having a hydrophilic group.
- an oleophilic group such as an alkyl group, an aryl group, an aralkyl group or an alkenyl group can be introduced in order to control the inking property.
- it can be performed by copolymerizing a lipophilic group-containing monomer such as an alkyl methacrylate ester.
- the binder polymer preferably has a mass average molar mass (Mw) of 2000 or more, more preferably 5000 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.
- a preferred example of the binder polymer is a polymer compound having a polyoxyalkylene chain in the side chain.
- a polymer compound having a polyoxyalkylene chain in the side chain hereinafter also referred to as a specific polymer compound
- the permeability of the fountain solution 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, novolak type phenol resin, polyester Examples thereof include resins, synthetic rubbers, and natural rubbers, and acrylic resins are particularly preferable.
- the specific polymer compound is substantially free of a perfluoroalkyl group.
- “Substantially free of perfluoroalkyl group” means that the mass ratio of fluorine atoms present as a perfluoroalkyl group in the polymer compound is less than 0.5% by mass, and preferably does not contain. The mass ratio of fluorine atoms is measured by elemental analysis.
- the “perfluoroalkyl group” is a group in which all hydrogen atoms of an alkyl group are substituted with fluorine atoms.
- 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 repeating alkylene oxides in the polyoxyalkylene chain, that is, the poly (alkylene oxide) site is preferably 2 to 50, and more preferably 4 to 25. If the number of alkylene oxide repeats is 2 or more, the permeability of the fountain solution is sufficiently improved, and if the number of repeats is 50 or less, the printing durability due to wear does not deteriorate, 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 the acrylic resin in a structure represented by the following general formula (1).
- y is preferably 2 to 50, and more preferably 4 to 25.
- R 1 represents a hydrogen atom or an alkyl group
- R 2 represents a hydrogen atom or an organic group.
- the organic group is preferably an alkyl group having 1 to 6 carbon atoms, and is a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, t-butyl group, n- Examples 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 1 is preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.
- R 2 is particularly preferably preferably atom
- the specific polymer compound may have crosslinkability in order 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.
- Examples of the polymer compound having an ethylenically unsaturated bond in the main chain of the molecule include poly-1,4-butadiene and poly-1,4-isoprene.
- polymer compound having an ethylenically unsaturated bond in the side chain of the molecule examples include an ester or amide polymer compound of acrylic acid or methacrylic acid, and an ester or amide residue (-COOR or CONHR Mention may be made of polymer compounds in which R) has an ethylenically unsaturated bond.
- X is a dicyclopentadienyl residue. Represents a group
- Specific examples of the amide residue include —CH 2 CH ⁇ CH 2 , —CH 2 CH 2 —Y (wherein Y represents a cyclohexene residue), —CH 2 CH 2 —OCO—CH ⁇ CH 2. Is mentioned.
- Specific polymer compounds having crosslinkability include, for example, free radicals (polymerization initiation radicals or growth radicals in the polymerization process of a polymerizable compound) added to the crosslinkable functional group, and directly or between the polymer compounds Addition polymerization is carried out through the polymerization chain to form a cross-link between the polymer compound molecules and cure.
- atoms in the polymer compound for example, hydrogen atoms on carbon atoms adjacent to the functional bridging group
- Crosslinks are formed between the compound molecules and harden.
- the content of the crosslinkable group in the specific polymer compound is preferably 0.1 to 10.0 mmol, more preferably 1 g per 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 copolymer component for the purpose of improving various performances such as image strength as long as the original effects of the specific polymer compound are not impaired.
- a copolymer component what is represented by the following general formula (2) can be mentioned.
- R 21 represents a hydrogen atom or a methyl group.
- R 22 represents a substituent.
- Preferable examples of R 22 include an ester group, an amide group, a cyano group, a hydroxy group, or an aryl group.
- the phenyl group which may have an ester group, an amide group, or a substituent is preferable.
- the substituent for the phenyl group include an alkyl group, an aralkyl group, an alkoxy group, and an acetoxymethyl group.
- Examples of the copolymer component represented by the general formula (2) include acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, N-substituted acrylamides, N-substituted methacrylamides, N, N -Substituted acrylamides, N, N-2-substituted methacrylamides, styrenes, acrylonitriles, methacrylonitriles and the like.
- acrylic esters methacrylic esters, acrylamides, methacrylamides, N-substituted acrylamides, N-substituted methacrylamides, N, N-2 substituted acrylamides, N, N-2 substituted methacrylamides And styrenes.
- Acrylonitrile is preferred from the viewpoint of printing durability.
- the ratio of the repeating unit having a poly (alkylene oxide) moiety to the total 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. %.
- A-1 to A-19 of the specific polymer compound are shown below, but the present invention is not limited thereto.
- the ratio of repeating units is a molar ratio.
- a hydrophilic polymer compound such as polyacrylic acid and polyvinyl alcohol described in JP-A-2008-195018 can be used in combination as required. Further, a lipophilic 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 exist in the form of fine particles, in addition to being present as a binder that functions as a binder for the image recording layer components.
- the average particle size is in the range of 10 to 1000 nm, preferably in the range of 20 to 300 nm, 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, based on the total solid content of the image recording layer. In the range of 3 to 90% by mass, the permeability of dampening water and the image formability can be more reliably achieved.
- a polymer compound having a polyfunctional thiol having 6 or more and 10 or less functions as a nucleus, a polymer chain bonded to the nucleus by a sulfide bond, and the polymer chain having a polymerizable group (Hereinafter also referred to as a star polymer compound).
- a star polymer compound for example, compounds described in JP2012-148555A 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 portion as described in JP-A-2008-195018, having a main chain or a side chain, preferably a side chain. What has in a chain
- strand is mentioned. Crosslinking is formed between the polymer molecules by the polymerizable group, and curing is accelerated.
- an ethylenically unsaturated group such as a (meth) acryl group, a vinyl group, an allyl group, or a styryl group, or an epoxy group is preferable, and a (meth) acryl group, a vinyl group, or a styryl group is polymerizable. More preferable from the viewpoint, and a (meth) acryl group is particularly preferable.
- These groups can be introduced into the polymer by polymer reaction or copolymerization.
- a reaction between a polymer having a carboxy group in the side chain and glycidyl methacrylate, or a reaction between 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, most preferably 0.5, per 1 g of the star polymer compound. ⁇ 5.5 mmol.
- the star polymer compound preferably further has a hydrophilic group.
- the hydrophilic group contributes to imparting on-press developability to the image recording layer.
- the coexistence of a polymerizable group and a hydrophilic group makes it possible to achieve both printing durability and developability.
- hydrophilic group examples include —SO 3 M 1 , —OH, —CONR 1 R 2 (M 1 represents hydrogen, metal ion, ammonium ion, phosphonium ion, and R 1 and R 2 each independently represents a hydrogen atom.
- M 1 represents hydrogen, metal ion, ammonium ion, phosphonium ion
- R 1 and R 2 each independently represents a hydrogen atom.
- —N + R 3 R 4 R 5 X — R 3 to R 5 are each independently represent an alkyl group having 1 to 8 carbon atoms, X - represents a counter anion
- n and m each independently represent an integer of 1 to 100, and R each independently represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms.
- star polymer compound is a star polymer compound having a polyoxyalkylene chain (for example, a group represented by the above general formula (1) or (2)) in the side chain
- a star polymer compound is also a polymer compound having the polyoxyalkylene chain in the side chain.
- hydrophilic groups —CONR 1 R 2 , a group represented by the general formula (1), and a group represented by the general formula (2) are preferable, and represented by —CONR 1 R 2 and the general formula (1)
- the group represented by the general formula (1) is particularly preferred.
- n is more preferably 1 to 10, and particularly preferably 1 to 4.
- R 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 preferably has substantially no carboxylic acid group, phosphoric acid group or 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 these acid groups are less than 0.1 mmol / g, developability is further improved.
- a lipophilic group such as an alkyl group, an aryl group, an aralkyl group, and an alkenyl group can be introduced into the star polymer compound in order to control the inking property.
- a lipophilic group-containing monomer such as alkyl methacrylate ester may be copolymerized.
- star polymer compound examples are shown below, but the present invention is not limited thereto.
- the structure corresponding to each number of the central core is the structure described in paragraph numbers [0021] to [0040] of JP 2012-148555 A, and the contents thereof are incorporated in the present specification.
- the polyfunctional thiol having 6 to 10 functional groups is used as a nucleus, but the present invention is not limited to this.
- the central core is pentafunctional or less. Also good.
- the star polymer compound can be synthesized by a known method such as radical polymerization of the monomer constituting the polymer chain in the presence of the polyfunctional thiol compound.
- the mass average molar mass (Mw) of the star polymer compound is preferably from 5,000 to 500,000, more preferably from 10,000 to 250,000, and particularly preferably from 20,000 to 150,000. In this range, the on-press developability and printing durability become better.
- star polymer compound may be used alone, or two or more types may be mixed and used. Moreover, you may use together with a normal linear binder polymer.
- the content of the star polymer compound is preferably 5 to 95% by mass, more preferably 10 to 90% by mass, and particularly preferably 15 to 85% by mass with respect to the total solid content of the image recording layer.
- the star polymer compound described in JP 2012-148555 A is preferable because the permeability of the fountain solution is promoted and the on-press developability is improved.
- the image recording layer A can contain other components described below as required.
- 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.
- a low molecular weight hydrophilic compound for example, as the water-soluble organic compound, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol and the like glycols and ether or ester derivatives thereof, glycerin, Polyols such as pentaerythritol and tris (2-hydroxyethyl) isocyanurate, organic amines such as triethanolamine, diethanolamine and monoethanolamine and salts thereof, organic sulfones such as alkylsulfonic acid, toluenesulfonic acid and benzenesulfonic acid Acids and salts thereof, organic sulfamic acids such as alkylsulfamic acid and salts thereof, organic sulfuric acids such as alkyl
- the salt may be a potassium salt or a lithium salt.
- organic sulfate examples include compounds described in paragraph numbers [0034] to [0038] of JP-A-2007-276454.
- betaines compounds in which the hydrocarbon substituent on the nitrogen atom has 1 to 5 carbon atoms are preferable.
- Specific examples include trimethylammonium acetate, dimethylpropylammonium acetate, 3-hydroxy-4-trimethyl.
- 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 even more preferable. In this range, good on-press developability and printing durability can be obtained.
- a compound may be used independently and may be used in mixture of 2 or more types.
- a grease sensitizer such as a phosphonium compound, a nitrogen-containing low molecular weight compound, or an ammonium group-containing polymer can be used in the image recording layer in order to improve the inking property.
- these compounds function as a surface coating agent for the inorganic stratiform compound, and have an effect of preventing a decrease in the inking property during printing by the inorganic stratiform compound.
- nitrogen-containing low molecular weight compounds include the compounds described in paragraph numbers [0021] to [0037] of JP-A-2008-284858 and paragraphs [0030] to [0057] of JP-A-2009-90645. It is done.
- the ammonium group-containing polymer may be any polymer having an ammonium group in its structure, but a polymer containing 5 to 80 mol% of a (meth) acrylate having an ammonium group in the side chain as a copolymerization component. preferable. Specific examples include the polymers described in paragraph numbers [0089] to [0105] of JP2009-208458A.
- the ammonium group-containing polymer has a reduced specific viscosity (unit: ml / g) determined by the following measurement method, preferably 5 to 120, more preferably 10 to 110, and more preferably 15 to Those in the range of 100 are particularly preferred.
- Mw mass average molar mass
- the content of the sensitizer is preferably 0.01 to 30.0% by mass, more preferably 0.1 to 15.0% by mass, and more preferably 1 to 10% by mass with respect to the total solid content of the image recording layer. Further preferred.
- the image recording layer includes, as other components, a surfactant, a colorant, a bake-out agent, a polymerization inhibitor, a higher fatty acid derivative, a plasticizer, inorganic fine particles, an inorganic layered compound, a co-sensitizer, A chain transfer agent and the like can be contained.
- a surfactant for example, paragraph numbers [0114] to [0159] of Japanese Patent Application Laid-Open No. 2008-284817, paragraph numbers [0023] to [0027] of Japanese Patent Application Laid-Open No. 2006-091479, and US Patent Publication No. 2008/0311520.
- paragraph numbers [0114] to [0159] of Japanese Patent Application Laid-Open No. 2008-284817, paragraph numbers [0023] to [0027] of Japanese Patent Application Laid-Open No. 2006-091479, and US Patent Publication No. 2008/0311520 The compound and the addition amount described in paragraph [0060] of FIG.
- the image recording layer is prepared by dispersing or dissolving the necessary components described above in a known solvent. It is formed by coating this on a support by a known method such as bar coater coating and drying.
- the coating amount (solid content) of the image recording layer on the support obtained after coating and drying is usually 0.3 to 3.0 g / m 2 although it varies depending on the application. Within this range, good sensitivity and good film characteristics of the image recording layer can be obtained.
- the image recording layer B contains an infrared absorber, a polymerization initiator, a polymerizable compound, and a polymer compound in the form of fine particles.
- an infrared absorber a polymerization initiator
- a polymerizable compound a polymerizable compound
- a polymer compound in the form of fine particles a polymer compound in the form of fine particles.
- the infrared absorber the polymerization initiator, and the polymerizable compound in the image recording layer B
- the infrared absorber, the polymerization initiator, and the polymerizable compound described in the image recording layer A can be similarly used.
- the polymer compound in the form of fine particles is selected from hydrophobic thermoplastic polymer fine particles, thermally reactive polymer fine particles, polymer fine particles having a polymerizable group, microcapsules enclosing a hydrophobic compound, and microgel (crosslinked polymer fine particles). It is preferable. Among these, polymer fine particles and microgels having a polymerizable group are preferable.
- the particulate polymeric compound comprises at least one ethylenically unsaturated polymerizable group. Due to the presence of such a polymer compound in the form of fine particles, the effect of improving the printing durability of the exposed portion and the on-press developability of the unexposed portion can be obtained.
- Hydrophobic thermoplastic polymer fine particles include Research Disclosure No. 1 of January 1992. 33303, hydrophobic thermoplastic polymer fine particles described in JP-A-9-123387, JP-A-9-131850, JP-A-9-171249, JP-A-9-171250 and European Patent 931647 are preferred. .
- polymer constituting the hydrophobic thermoplastic polymer fine particle examples include ethylene, styrene, vinyl chloride, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, vinylidene chloride, acrylonitrile, vinyl carbazole, polyalkylene structure Mention may be made of homopolymers or copolymers of monomers such as acrylates or methacrylates or mixtures thereof. Preferable examples include a copolymer containing polystyrene, styrene and acrylonitrile, and polymethyl methacrylate.
- the average particle diameter of the hydrophobic thermoplastic polymer fine particles is preferably 0.01 to 3.0 ⁇ m.
- thermoreactive polymer fine particles examples include polymer fine particles having a heat-reactive group.
- the thermoreactive polymer fine particles form a hydrophobized region by crosslinking by a thermal reaction and a functional group change at that time.
- the thermally reactive group in the polymer fine particles having a thermally reactive group may be any functional group that performs any reaction as long as a chemical bond is formed, but is preferably a polymerizable group.
- Ethylenically unsaturated group for example, acryloyl group, methacryloyl group, vinyl group, allyl group, etc.
- cationic polymerizable group for example, vinyl group, vinyloxy group, epoxy group, oxetanyl group, etc.
- addition reaction for radical polymerization reaction An isocyanate group or a block thereof, an epoxy group, a vinyloxy group and a functional group having an active hydrogen atom as a reaction partner thereof (for example, an amino group, a hydroxy group, a carboxy group, etc.) Hydroxy group or amino group that is the reaction partner, acid anhydride that performs the ring-opening addition reaction, and a reaction partner that is Such as amino group or hydroxy group are preferably exemplified.
- the microcapsules for example, as described in JP-A Nos. 2001-277740 and 2001-277742, at least a part of the constituent components of the image recording layer is encapsulated in the microcapsules.
- the constituent components of the image recording layer can also be contained outside the microcapsules.
- the image recording layer containing a microcapsule is preferably configured so that a hydrophobic constituent component is encapsulated in the microcapsule and a hydrophilic constituent component is contained outside the microcapsule.
- the microgel (crosslinked polymer fine particles) can contain a part of the constituent components of the image recording layer on at least one of the surface or the inside thereof.
- a reactive microgel having a radical polymerizable group on its surface is preferable from the viewpoint of image forming sensitivity and printing durability.
- a well-known method can be applied to microencapsulate or microgel the constituent components of the image recording layer.
- the average particle size of the polymer compound in the form of fine particles is preferably 0.01 to 3.0 ⁇ m, more preferably 0.03 to 2.0 ⁇ m, and still more preferably 0.10 to 1.0 ⁇ m. In this range, good resolution and stability over time can be obtained.
- the content of the polymer compound in the form of fine particles is preferably 5 to 90% by mass based on the total solid content of the image recording layer.
- the image recording layer B can contain other components described in the image recording layer A as necessary.
- the image recording layer C contains an infrared absorber and a thermoplastic fine particle polymer.
- the components of the image recording layer C will be described.
- the infrared absorber contained in the image recording layer C is preferably a dye or pigment having an absorption maximum of 760 to 1200 nm. A dye is more preferred.
- the dye examples include commercially available dyes and literature (for example, “Dye Handbook” edited by the Society of Synthetic Organic Chemistry, published in 1970, “Chemical Industry”, May 1986, pages 45-51, “Near-Infrared Absorbing Dye”, “90 Development and market trends of age functional pigments "Chapter 2 Section 2.3 (CMC Publishing, published in 1990) or patents can be used.
- Specific examples include azo dyes and metal complex azo dyes. Infrared absorbing dyes such as pyrazolone azo dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, polymethine dyes and cyanine dyes are preferred.
- a particularly preferable dye to be added to the image recording layer is an infrared absorbing dye having a water-soluble group.
- Specific examples of the infrared absorbing dye are shown below, but the present invention is not limited thereto.
- pigments examples include commercially available pigment and color index (CI) manuals, “Latest Pigment Handbook” (edited by the Japan Pigment Technology Association, published in 1977), “Latest Pigment Applied Technology” (published by CMC, published in 1986), “Printing” The pigments described in “Ink Technology” (CMC Publishing, 1984) can be used.
- CI pigment and color index
- the particle diameter of the pigment is preferably 0.01 to 1 ⁇ m, more preferably 0.01 to 0.5 ⁇ m.
- a method for dispersing the pigment a known dispersion technique used in ink production, toner production, or the like can be used. Details are described in "Latest Pigment Applied Technology” (CMC Publishing, 1986).
- the content of the infrared absorber is preferably from 0.1 to 30% by mass, more preferably from 0.25 to 25% by mass, and particularly preferably from 0.5 to 20% by mass based on the solid content of the image recording layer. Within this range, good sensitivity can be obtained without impairing the film strength of the image recording layer.
- the thermoplastic fine particle polymer preferably has a glass transition temperature (Tg) of 60 ° C to 250 ° C.
- Tg of the thermoplastic fine particle polymer is more preferably from 70 ° C to 140 ° C, and further preferably from 80 ° C to 120 ° C.
- Examples of the thermoplastic fine particle polymer having a Tg of 60 ° C. or higher include Research Disclosure No. 1 of January 1992. 33303, JP-A-9-123387, JP-A-9-131850, JP-A-9-171249, JP-A-9-171250, and EP931647, and the like. it can.
- homopolymers or copolymers composed of monomers such as ethylene, styrene, vinyl chloride, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, vinylidene chloride, acrylonitrile, vinyl carbazole, or mixtures thereof Etc. can be illustrated.
- Preferred examples include polystyrene and polymethyl methacrylate.
- the average particle size of the thermoplastic fine particle polymer is preferably 0.005 to 2.0 ⁇ m. If the average particle size is too large, the resolution may be deteriorated, and if it is too small, the temporal stability may be deteriorated. This value is also applied as an average particle diameter when two or more thermoplastic fine particle polymers are mixed.
- the average particle diameter is more preferably 0.01 to 1.5 ⁇ m, particularly preferably 0.05 ⁇ m to 1.0 ⁇ m.
- the polydispersity when two or more thermoplastic fine particle polymers are mixed is preferably 0.2 or more. The average particle size and polydispersity are calculated by laser light scattering.
- thermoplastic fine particle polymers Two or more kinds may be mixed and used. Specifically, at least two kinds of uses having different particle sizes or at least two kinds of uses having different Tg may be mentioned. By using two or more types in combination, the film curability of the image area is further improved, and the printing durability is further improved when a lithographic printing plate is used. For example, when thermoplastic particles having the same particle size are used as the thermoplastic fine particle polymer, there will be a certain amount of voids between the thermoplastic fine particle polymers, and even if the thermoplastic fine particle polymer is melted and solidified by image exposure, Curability may not be as desired.
- thermoplastic fine particle polymer having a different particle size when used, the porosity between the thermoplastic fine particle polymers can be lowered, and as a result, the film curability of the image area after image exposure can be reduced. Can be improved.
- thermoplastic fine particle polymer when the same Tg is used as the thermoplastic fine particle polymer, when the temperature rise of the image recording layer due to image exposure is insufficient, the thermoplastic fine particle polymer is not sufficiently melted and solidified, and the curability of the film is desired. It may not be a thing. In contrast, when a thermoplastic fine particle polymer having a different Tg is used, the film curability of the image area can be improved even when the temperature rise of the image recording layer due to image exposure is insufficient.
- thermoplastic fine particle polymer When two or more kinds of thermoplastic fine particle polymers having different Tg are mixed and used, at least one Tg of the thermoplastic fine particle polymer is preferably 60 ° C. or higher. Under the present circumstances, it is preferable that the difference of Tg is 10 degreeC or more, More preferably, it is 20 degreeC or more. Further, it is preferable to contain 70% by mass or more of the thermoplastic fine particle polymer having a Tg of 60 ° C. or higher based on the total thermoplastic fine particle polymer.
- the thermoplastic fine particle polymer may have a crosslinkable group.
- the crosslinkable group is thermally reacted by the heat generated in the image exposed area to form a crosslink between the polymers, the film strength of the image area is improved, and the printing durability is increased. Will be better.
- the crosslinkable group may be any functional group capable of performing any reaction as long as a chemical bond is formed.
- an ethylenically unsaturated group that performs a polymerization reaction for example, acryloyl group, methacryloyl group, vinyl group, allyl group, etc.
- An isocyanate group that performs an addition reaction, or a block thereof and a group having an active hydrogen atom that is a reaction partner for example, an amino group, a hydroxy group, a carboxyl group, etc.
- an epoxy group that also performs an addition reaction, and a reaction partner thereof
- examples thereof include an amino group, a carboxyl group or a hydroxy group, a carboxyl group and a hydroxy group or an amino group that perform a condensation reaction, an acid anhydride that performs a ring-opening addition reaction, an amino group or a hydroxy group, and the like.
- thermoplastic fine particle polymer having a crosslinkable group examples include acryloyl group, methacryloyl group, vinyl group, allyl group, epoxy group, amino group, hydroxy group, carboxyl group, isocyanate group, acid anhydride and the like.
- examples thereof include those having a crosslinkable group such as a group in which the above is protected.
- the introduction of these crosslinkable groups into the polymer may be performed during the polymerization of the fine particle polymer, or may be performed using a polymer reaction after the polymerization of the fine particle polymer.
- a crosslinkable group is introduced during the polymerization of the fine particle polymer, it is preferable to carry out emulsion polymerization or suspension polymerization of the monomer having a crosslinkable group.
- the monomer having a crosslinkable group include allyl methacrylate, allyl acrylate, vinyl methacrylate, vinyl acrylate, glycidyl methacrylate, glycidyl acrylate, 2-isocyanate ethyl methacrylate, or a block isocyanate based on alcohol thereof, 2-isocyanate ethyl acrylate or the like.
- Examples of the polymer reaction used when the crosslinkable group is introduced after the polymerization of the fine particle polymer include the polymer reaction described in WO96 / 34316.
- the thermoplastic fine particle polymer may react with each other through a crosslinkable group, or may react with a high molecular compound or a low molecular compound added to the image recording layer.
- the content of the thermoplastic fine particle polymer is preferably 50 to 95% by mass, more preferably 60 to 90% by mass, and particularly preferably 70 to 85% by mass based on the solid content of the image recording layer.
- the image recording layer C may further contain other components as necessary.
- ⁇ Surfactant having polyoxyalkylene group or hydroxy group As a surfactant having a polyoxyalkylene group (hereinafter also referred to as POA group) or a hydroxy group, a surfactant having a POA group or a hydroxy group can be used as appropriate, but an anionic surfactant or nonionic surfactant is used. Agents are preferred. Among the anionic surfactants or nonionic surfactants having a POA group or a hydroxy group, anionic surfactants or nonionic surfactants having a POA group are preferred.
- a polyoxyethylene group a polyoxypropylene group, a polyoxybutylene group and the like are preferable, and a polyoxyethylene group is particularly preferable.
- the average degree of polymerization of the oxyalkylene group is usually from 2 to 50, preferably from 2 to 20.
- the number of hydroxy groups is usually 1 to 10 and preferably 2 to 8. However, the terminal hydroxy group in the oxyalkylene group is not included in the number of hydroxy groups.
- the anionic surfactant having a POA group is not particularly limited, and polyoxyalkylene alkyl ether carboxylates, polyoxyalkylene alkyl sulfosuccinates, polyoxyalkylene alkyl ether sulfates, alkylphenoxy polyoxyalkylene propyl sulfonic acids Salts, polyoxyalkylene alkyl sulfophenyl ethers, polyoxyalkylene aryl ether sulfates, polyoxyalkylene polycyclic phenyl ether sulfates, polyoxyalkylene styryl phenyl ether sulfates, polyoxyalkylene alkyl ether phosphates, Polyoxyalkylene alkyl phenyl ether phosphate ester salt, polyoxyalkylene perfluoroalkyl ether Ester salts and the like.
- the anionic surfactant having a hydroxy group is not particularly limited, and examples thereof include hydroxycarboxylates, hydroxyalkyl ether carboxylates, hydroxyalkanesulfonates, fatty acid monoglyceride sulfates, and fatty acid monoglyceride phosphates. .
- the content of the surfactant having a POA group or a hydroxy group is preferably 0.05 to 15% by mass, more preferably 0.1 to 10% by mass, based on the solid content of the image recording layer.
- surfactant having a POA group or a hydroxy group are given below, but the present invention is not limited thereto.
- the following surfactant A-12 is available from DuPont under the trade name Zonyl FSP.
- the following surfactant N-11 is available from DuPont under the trade name Zonyl FSO 100.
- the image recording layer may contain an anionic surfactant having no polyoxyalkylene group and hydroxy group for the purpose of ensuring the uniformity of application of the image recording layer.
- the anionic surfactant is not particularly limited as long as the above object is achieved.
- alkylbenzenesulfonic acid or a salt thereof, alkylnaphthalenesulfonic acid or a salt thereof, (di) alkyldiphenyl ether (di) sulfonic acid or a salt thereof, or an alkyl sulfate ester salt is preferable.
- the addition amount of the anionic surfactant having no polyoxyalkylene group and hydroxy group is preferably 1 to 50% by mass, more preferably 1 to 30% by mass with respect to the surfactant having a polyoxyalkylene group or hydroxy group. preferable.
- anionic surfactant having no polyoxyalkylene group and hydroxy group are listed below, but the present invention is not limited thereto.
- a nonionic surfactant having no polyoxyalkylene group and hydroxy group or a fluorine-based surfactant may be used.
- a fluorosurfactant described in JP-A No. 62-170950 is preferably used.
- the image recording layer can contain a hydrophilic resin.
- the hydrophilic resin include hydrophilic groups such as hydroxy group, hydroxyethyl group, hydroxypropyl group, amino group, aminoethyl group, aminopropyl group, carboxyl group, carboxylate group, sulfo group, sulfonate group, and phosphate group.
- the resin it has is preferable.
- hydrophilic resins include gum arabic, casein, gelatin, starch derivatives, carboxymethylcellulose and its sodium salt, cellulose acetate, sodium alginate, vinyl acetate-maleic acid copolymers, styrene-maleic acid copolymers, polyacrylic acids and Salts thereof, polymethacrylic acids and salts thereof, homopolymers and copolymers of hydroxyethyl methacrylate, homopolymers and copolymers of hydroxyethyl acrylate, homopolymers and copolymers of hydroxypropyl methacrylate, homopolymers and copolymers of hydroxypropyl acrylate, hydroxybutyl Methacrylate homopolymers and copolymers, hydroxybutyl acrylate homopolymers and copolymers, polyesters Lenglycols, hydroxypropylene polymers, polyvinyl alcohols, hydrolyzed polyvinyl acetate having a degree of hydrolysis of at least 60%,
- the molecular weight of the hydrophilic resin is preferably 2000 or more. If it is less than 2000, sufficient film strength and printing durability cannot be obtained, which is not preferable.
- the content of the hydrophilic resin is preferably 0.5 to 50% by mass, more preferably 1 to 30% by mass, based on the solid content of the image recording layer.
- the image recording layer may contain inorganic fine particles.
- Preferred examples of the inorganic fine particles include silica, alumina, magnesium oxide, titanium oxide, magnesium carbonate, calcium alginate, and a mixture thereof.
- the inorganic fine particles can be used for the purpose of strengthening the film.
- the average particle size of the inorganic fine particles is preferably 5 nm to 10 ⁇ m, more preferably 10 nm to 1 ⁇ m. Within this range, it is possible to form a non-image portion having excellent hydrophilicity that is stably dispersed with the thermoplastic fine particle polymer, sufficiently retains the film strength of the image recording layer, and hardly causes printing stains.
- the inorganic fine particles can be easily obtained as a commercial product such as a colloidal silica dispersion.
- the content of the inorganic fine particles is preferably 1.0 to 70% by mass, more preferably 5.0 to 50% by mass, based on the solid content of the image recording layer.
- the image recording layer can contain a plasticizer in order to impart flexibility and the like of the coating film.
- the plasticizer include polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, and the like. It is done.
- the content of the plasticizer is preferably 0.1% to 50% by mass, more preferably 1 to 30% by mass, based on the solid content of the image recording layer.
- a compound that initiates or accelerates the reaction of the heat-reactive functional group is added as necessary. be able to.
- the compound that initiates or accelerates the reaction of the thermoreactive functional group include compounds that generate radicals or cations by heat. Examples thereof include lophine dimer, trihalomethyl compound, peroxide, azo compound, diazonium salt, onium salt including diphenyliodonium salt, acylphosphine, imide sulfonate and the like.
- the amount of such a compound added is preferably 1 to 20% by mass, more preferably 1 to 10% by mass, based on the solid content of the image recording layer. Within this range, good reaction initiation or acceleration effect can be obtained without impairing on-press developability.
- the image recording layer is formed by dissolving or dispersing the necessary components described above in an appropriate solvent to prepare a coating solution, and coating the support.
- a solvent water or a mixed solvent of water and an organic solvent is used, and mixed use of water and an organic solvent is preferable in terms of improving the surface state after coating.
- the amount of the organic solvent varies depending on the type of the organic solvent, and cannot be generally specified, but is usually preferably 5 to 50% by volume in the mixed solvent. However, it is necessary to use the organic solvent in such an amount that the thermoplastic fine particle polymer does not aggregate.
- the solid content concentration of the image recording layer coating solution is preferably 1 to 50% by mass.
- the organic solvent used as the solvent for the coating solution is preferably an organic solvent that is soluble in water.
- alcohol solvents such as methanol, ethanol, propanol, isopropanol, 1-methoxy-2-propanol, ketone solvents such as acetone and methyl ethyl ketone, glycol ether solvents such as ethylene glycol dimethyl ether, ⁇ -butyrolactone, N, N—
- Examples include dimethylformamide, N, N-dimethylacetamide, tetrahydrofuran, dimethyl sulfoxide and the like.
- an organic solvent having a boiling point of 120 ° C. or less and a solubility in water (amount dissolved in 100 g of water) of 10 g or more is preferable, and an organic solvent of 20 g or more is more preferable.
- the coating amount (solid content) of the image recording layer on the support obtained after coating and drying varies depending on the use, but is usually preferably 0.5 to 5.0 g / m 2 , preferably 0.5 to 2.0 g / m 2. m 2 is more preferable.
- planographic printing plate precursor The following describes other components of the planographic printing plate precursor.
- the lithographic printing plate precursor is preferably provided with an undercoat layer (sometimes referred to as an intermediate layer) between the image recording layer and the support.
- the undercoat layer enhances the adhesion between the support and the image recording layer in the exposed area and easily peels from the support of the image recording layer in the unexposed area. Contributes to improving the performance.
- the undercoat layer functions as a heat insulating layer, thereby preventing the heat generated by the exposure from diffusing to the support and lowering the sensitivity.
- the compound used for the undercoat layer include a silane coupling agent having an addition polymerizable ethylenic double bond reactive group described in JP-A-10-282679, Examples thereof include phosphorus compounds having an ethylenic double bond reactive group described in Japanese Patent No. 304441.
- Preferable examples include polymer compounds having an adsorptive group, a hydrophilic group, and a crosslinkable group that can be adsorbed on the surface of the support, as described in JP-A Nos. 2005-125749 and 2006-188038. It is done.
- Such a polymer compound is preferably a copolymer of a monomer having an adsorptive group, a monomer having a hydrophilic group, and a monomer having a crosslinkable group. More specifically, it has an adsorbing group such as a phenolic hydroxy group, a carboxy group, —PO 3 H 2 , —OPO 3 H 2 , —CONHSO 2 —, —SO 2 NHSO 2 —, —COCH 2 COCH 3, etc.
- an adsorbing group such as a phenolic hydroxy group, a carboxy group, —PO 3 H 2 , —OPO 3 H 2 , —CONHSO 2 —, —SO 2 NHSO 2 —, —COCH 2 COCH 3, etc.
- Examples thereof include a copolymer of a monomer, a monomer having a hydrophilic group such as a sulfo group, and a monomer having a polymerizable crosslinkable group such as a methacryl group or an allyl group.
- the polymer compound may have a crosslinkable group introduced by salt formation between a polar substituent of the polymer compound, a substituent having a counter charge and a compound having an ethylenically unsaturated bond.
- monomers other than those described above, preferably hydrophilic monomers may be further copolymerized.
- the content of unsaturated double bonds in the polymer compound for the 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 polymer compound for the undercoat layer preferably has a mass average molar mass of 5000 or more, more preferably 10,000 to 300,000.
- the undercoat layer is a chelating agent, a secondary or tertiary amine, a polymerization inhibitor, an amino group, or a functional group having a polymerization inhibiting ability and an aluminum support for preventing contamination over time.
- Compounds having a group that interacts with the surface for example, 1,4-diazabicyclo [2,2,2] octane (DABCO), 2,3,5,6-tetrahydroxy-p-quinone, chloranil, sulfophthalic acid , Hydroxyethylethylenediaminetriacetic acid, dihydroxyethylethylenediaminediacetic acid, hydroxyethyliminodiacetic acid, and the like.
- the undercoat layer is applied by a known method.
- the coating amount (solid content) of the undercoat layer is preferably 0.1 ⁇ 100mg / m 2, and more preferably 1 ⁇ 30mg / m 2.
- a known support is used as the support for the lithographic printing plate precursor.
- an aluminum plate that has been roughened and anodized by a known method is preferred.
- the support preferably has a center line average roughness of 0.10 to 1.2 ⁇ m.
- a protective layer In the planographic printing plate precursor, a protective layer (overcoat layer) is preferably provided on the image recording layer.
- the protective layer In addition to the function of suppressing the image formation inhibition reaction by blocking oxygen, the protective layer has a function of preventing scratches in the image recording layer and preventing ablation during high-illuminance laser exposure.
- the protective layer having such characteristics is described in, for example, US Pat. No. 3,458,311 and Japanese Patent Publication No. 55-49729.
- the low oxygen permeability polymer 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 necessary. it can.
- Specific examples include polyvinyl alcohol, modified polyvinyl alcohol, polyvinyl pyrrolidone, water-soluble cellulose derivatives, poly (meth) acrylonitrile, and the like.
- modified polyvinyl alcohol acid-modified polyvinyl alcohol having a carboxy group or a sulfo group is preferably used.
- modified polyvinyl alcohols described in JP-A-2005-250216 and JP-A-2006-259137 are preferable.
- the protective layer preferably contains an inorganic stratiform compound such as natural mica and synthetic mica as described in JP-A-2005-119273 in order to enhance oxygen barrier properties.
- an inorganic stratiform compound such as natural mica and synthetic mica as described in JP-A-2005-119273 in order to enhance oxygen barrier properties.
- the protective layer contains a polysaccharide.
- polysaccharides include starch derivatives (eg, dextrin, enzymatically degraded dextrin, hydroxypropylated starch, carboxymethylated starch, phosphate esterified starch, polyoxyalkylene grafted starch, cyclodextrin), celluloses (eg, carboxymethylcellulose, carboxy Ethyl cellulose, methyl cellulose, hydroxypropyl cellulose, methylpropyl cellulose and the like), carrageenan, alginic acid, guar gum, locust bean gum, xanthan gum, gum arabic, soybean polysaccharide and the like.
- starch derivatives eg, dextrin, enzymatically degraded dextrin, hydroxypropylated starch, carboxymethylated starch, phosphate esterified starch, polyoxyalkylene grafted starch, cyclodextrin
- celluloses
- the protective layer can contain known additives such as a plasticizer for imparting flexibility, a surfactant for improving coating properties, and inorganic fine particles for controlling the slipperiness of the surface. Further, the protective layer can contain the sensitizer described in the description of the image recording layer.
- the protective layer is applied by a known method.
- 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.
- the lithographic printing plate precursor used in the processing method according to the present invention preferably has a sagging shape at the end.
- the use of a lithographic printing plate precursor having a sag shape at the end is useful for preventing edge contamination in combination with the processing method according to the present invention.
- FIG. 1 is a diagram schematically showing a cross-sectional shape of a lithographic printing plate precursor.
- a planographic printing plate precursor 1 has a sag 2 at its end.
- the distance X between the upper end of the end surface 1c of the lithographic printing plate precursor 1 (the boundary point between the sag 2 and the end surface 1c) and the extension line of the image recording layer surface (protective layer surface when a protective layer is formed) 1a is expressed as “ It is called “sag amount”, and the distance Y between the point at which the image recording layer surface 1a of the planographic printing plate precursor 1 begins to sag and the extended line of the end surface 1c is called “sag width”.
- the amount of sagging at the edge of the lithographic printing plate precursor is preferably 35 ⁇ m or more.
- the upper limit of the sagging amount is preferably 150 ⁇ m.
- the sagging amount exceeds 150 ⁇ m, the surface state of the end portion is significantly deteriorated and the on-press developability is deteriorated.
- the sag amount is in the range of 35 to 150 ⁇ m, if the sag width is small, cracks are generated at the end portions, and the printing ink accumulates there, causing stains.
- the sagging width is suitably in the range of 50 to 300 ⁇ m, and preferably in the range of 70 to 250 ⁇ m.
- the preferable range of the sag amount and the sag width is not related to the edge shape of the support surface 1 b of the lithographic printing plate precursor 1.
- the boundary B between the image recording layer and the support and the support surface 1b are also sagged as in the image recording layer surface 1a.
- FIG. 2 is a cross-sectional view showing a cutting portion of a slitter device.
- a pair of upper and lower cutting blades 10 and 20 are arranged on the left and right.
- the cutting blades 10 and 20 are round blades on a circular plate, and the upper cutting blades 10a and 10b are supported on the rotating shaft 11 and the lower cutting blades 20a and 20b are supported on the rotating shaft 21 on the same axis.
- the upper cutting blades 10a and 10b and the lower cutting blades 20a and 20b are rotated in opposite directions.
- the planographic printing plate precursor 30 is cut into a predetermined width by passing between the upper cutting blades 10a and 10b and the lower cutting blades 20a and 20b.
- JP-A-8-58257 For the cutting of the lithographic printing plate precursor, methods described in JP-A-8-58257, JP-A-9-211843, JP-A-10-10056, and JP-A-11-52579 can be used.
- the image exposure of the on-press development type lithographic printing plate precursor in the processing method according to the present invention can be performed according to the image exposure operation of a normal on-press development type lithographic printing plate precursor.
- Image exposure is performed by laser exposure through a transparent original having a line image, a halftone dot image, or the like, or by laser light scanning using digital data.
- the wavelength of the light source is preferably 700 to 1400 nm.
- a solid-state laser and a semiconductor laser that emit infrared rays are suitable.
- the output is preferably 100 mW or more
- the exposure time per pixel is preferably within 20 microseconds
- the irradiation energy amount is preferably 10 to 300 mJ / cm 2 .
- the exposure mechanism may be any of an internal drum system, an external drum system, a flat bed system, and the like. Image exposure can be performed by a conventional method using a plate setter or the like.
- On-press development and printing of a lithographic printing plate precursor in which a treatment liquid containing a hydrophilizing agent is applied to the edge region can be performed by conventional methods. That is, when a lithographic printing plate precursor coated with a treatment liquid containing a hydrophilizing agent is applied to the end region of the printing plate cylinder (cylinder) of a printing press and dampening water and printing ink are supplied, the image recording layer In the exposed portion, the image recording layer cured by exposure forms a printing ink receiving portion having an oleophilic surface.
- the uncured image recording layer is removed by dissolution or dispersion by the supplied dampening water and / or printing ink, and a hydrophilic surface is exposed in that area.
- the fountain solution adheres to the exposed hydrophilic surface, and the printing ink is deposited on the image recording layer in the exposed area and printing is started.
- the surface of the lithographic printing plate precursor may be supplied first with dampening water or printing ink.
- the dampening water is first supplied. Is preferably supplied.
- the molecular weight is a mass average molar mass (Mw), and the ratio of repeating units is a mole percentage, except for those specifically defined.
- Preparation of lithographic printing plate precursor I (1) Preparation of support In order to remove rolling oil on the surface of an aluminum plate (material JIS A 1050) having a thickness of 0.3 mm, degreasing treatment was performed at 50 ° C. for 30 seconds using a 10 mass% sodium aluminate aqueous solution. After that, the aluminum surface was grained using three bundle-planted nylon brushes having a bristle diameter of 0.3 mm and a pumice-water suspension (specific gravity 1.1 g / cm 3 ) having a median diameter of 25 ⁇ m and washed thoroughly with water. .
- This aluminum plate was etched by being immersed in a 25 mass% sodium hydroxide aqueous solution at 45 ° C for 9 seconds, washed with water, further immersed in a 20 mass% nitric acid aqueous solution at 60 ° C for 20 seconds, and washed with water. At this time, the etching amount of the grained surface was about 3 g / m 2 .
- an electrochemical roughening treatment was performed continuously using an alternating voltage of 60 Hz.
- the electrolytic solution at this time was a 1% by mass nitric acid aqueous solution (containing 0.5% by mass of aluminum ions) and a liquid temperature of 50 ° C.
- the AC power source waveform is electrochemical roughening treatment using a trapezoidal rectangular wave alternating current with a time ratio TP of 0.8 msec until the current value reaches a peak from zero, a duty ratio of 1: 1, and a trapezoidal rectangular wave alternating current. Went. Ferrite was used for the auxiliary anode.
- the current density was 30 A / dm 2 at the peak current value, and 5% of the current flowing from the power source was shunted to the auxiliary anode.
- the amount of electricity in nitric acid electrolysis was 175 C / dm 2 when the aluminum plate was the anode. Then, water washing by spraying was performed.
- nitric acid electrolysis was performed with an aqueous solution of 0.5% by mass of hydrochloric acid (containing 0.5% by mass of aluminum ions) and an electrolytic solution having a liquid temperature of 50 ° C. under the condition of an electric quantity of 50 C / dm 2 when the aluminum plate was the anode.
- Electrochemical surface roughening treatment was carried out in the same manner as above, followed by washing with water by spraying.
- a 2.5 g / m 2 direct current anodic oxide film having a current density of 15 A / dm 2 was provided on the plate as a 15% by weight sulfuric acid aqueous solution (containing 0.5% by weight of aluminum ions) as an electrolyte, followed by washing with water.
- a support (1) was prepared. Thereafter, in order to ensure the hydrophilicity of the non-image area, the support (1) was subjected to a silicate treatment at 60 ° C. for 10 seconds using an aqueous 2.5 mass% No. 3 sodium silicate solution, and then washed with water for support. Body (2) was obtained. The adhesion amount of Si was 10 mg / m 2 . The center line average roughness (Ra) of the support (2) was measured using a needle having a diameter of 2 ⁇ m and found to be 0.51 ⁇ m.
- undercoat layer coating solution (1) having the following composition is applied onto the support (2) so that the dry coating amount is 20 mg / m 2 to have an undercoat layer.
- a support was prepared.
- the image recording layer coating solution (1) having the following composition was bar-coated on the undercoat layer formed as described above, and then oven-dried at 100 ° C for 60 seconds to obtain a dry coating amount. An image recording layer of 1.0 g / m 2 was formed.
- the image recording layer coating solution (1) was prepared by mixing and stirring the following photosensitive solution (1) and microgel solution (1) immediately before coating.
- the preparation method of the microgel (1) is shown below.
- microgel (1) As an oil phase component, trimethylolpropane and xylene diisocyanate adduct (Mitsui Chemical Polyurethane Co., Ltd., Takenate D-110N) 10 g, pentaerythritol triacrylate (Nippon Kayaku Co., Ltd., SR444) 3.15 g, And 0.1 g of Pionein A-41C (manufactured by Takemoto Yushi Co., Ltd.) was dissolved in 17 g of ethyl acetate.
- Trimethylolpropane and xylene diisocyanate adduct Mitsubishi Chemical Polyurethane Co., Ltd., Takenate D-110N
- pentaerythritol triacrylate Nippon Kayaku Co., Ltd., SR444
- Pionein A-41C manufactured by Takemoto Yushi Co., Ltd.
- aqueous phase component 40 g of a 4% by mass aqueous solution of polyvinyl alcohol (PVA-205, manufactured by Kuraray Co., Ltd.) was prepared.
- the oil phase component and the aqueous 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, stirred at room temperature for 30 minutes, and then stirred at 50 ° C. for 3 hours.
- a microgel (1) was prepared by diluting the solid content concentration of the microgel solution thus obtained with distilled water so as to be 15% by mass.
- the average particle size of the microgel was measured by a light scattering method and found to be 0.2 ⁇ m.
- the protective layer coating solution (1) having the following composition was bar-coated on the image recording layer, it was oven-dried at 120 ° C. for 60 seconds to obtain a dry coating amount of 0.15 g / m 2 .
- a protective layer was formed to prepare a lithographic printing plate precursor I.
- CKS50 Sulfonic acid modification, saponification degree 99 mol% or more, polymerization degree 300 0.10 g of 6% by weight aqueous solution ⁇ Polyvinyl alcohol (PVA-405 manufactured by Kuraray Co., Ltd.) Degree of saponification 81.5 mol%, degree of polymerization 500) 6% by weight aqueous solution 0.03 g ⁇ Surfactant (Emalex 710, trade name: manufactured by Nippon Emulsion Co., Ltd.) 1% by weight aqueous solution 0.86g ⁇ Ion-exchanged water 6.0g
- the aluminum plate was desmutted by etching with 155 g / l sulfuric acid aqueous solution at 70 ° C. for 4 seconds, and washed with demineralized water at 25 ° C. for 2 seconds.
- the aluminum plate was anodized in a 155 g / l sulfuric acid aqueous solution for 13 seconds at a temperature of 45 ° C. and a current density of 22 A / dm 2 and washed with demineralized water for 2 seconds. Further, it was treated with a 4 g / l aqueous polyvinylphosphonic acid solution at 40 ° C. for 10 seconds, washed with desalted water at 20 ° C. for 2 seconds, and dried.
- the support thus obtained had a surface roughness Ra of 0.21 ⁇ m and an anodized film amount of 4 g / m 2 .
- lithographic printing plate precursor An aqueous coating solution for an image recording layer containing the following thermoplastic fine particle polymer, infrared absorber and polyacrylic acid is prepared, and after adjusting the pH to 3.6, it is coated on the support, and at 50 ° C. for 1 minute. An image recording layer was formed by drying to prepare a lithographic printing plate precursor II. The coating amount after drying of each component is shown below.
- Thermoplastic fine particle polymer 0.7 g / m 2
- Infrared absorber IR-01 0.104 g / m 2
- Polyacrylic acid 0.09 g / m 2
- thermoplastic fine particle polymer used in the coating solution for the image recording layer are as shown below.
- Thermoplastic fine particle polymer styrene / acrylonitrile copolymer (molar ratio 50/50), Tg: 99 ° C., average particle size: 60 nm
- Polyacrylic acid mass average molecular weight: 250,000
- the particle size distribution of the polymer compound fine particles had a maximum value at a particle size of 150 nm.
- the particle size distribution is obtained by taking an electron micrograph of polymer compound fine particles, measuring the total particle size of 5000 particles on the photograph, and between 0 and the maximum value of the obtained particle size measurement value.
- the frequency of appearance of each particle size was plotted by dividing it into 50 logarithmic scales.
- the particle size of spherical particles having the same particle area as that on the photograph was used as the particle size.
- the shape measurement of the cut lithographic printing plate precursor was performed using a surface roughness meter (Surfcom) manufactured by Tokyo Seimitsu Co., Ltd.
- a model 480A was used as the surface roughness meter, and a stylus having a diameter of 2 ⁇ m was used.
- the shape was measured by moving the stylus from about 1 mm inside the lithographic printing plate precursor edge to the edge at a speed of 3 mm / sec, the sag amount was 60 ⁇ m and the sag width was 100 ⁇ m.
- the lithographic printing plate precursor was exposed with a Luxel PLANETSETTER T-6000III equipped with an infrared semiconductor laser under the conditions of an outer drum rotation speed of 1000 rpm, a laser output of 70%, and a resolution of 2400 dpi.
- the exposed image includes a solid image and a 50% halftone dot chart.
- Treatment liquids A to I were prepared by dissolving the compounds listed in Table 1 below in pure water. The number in parentheses represents the concentration (% by mass) of the compound.
- Table 1 the compounds described by trade names are as follows. ⁇ New Coal B13 (Nonionic surfactant, polyoxyethylene aryl ether, manufactured by Nippon Emulsifier Co., Ltd.) ⁇ Perex NBL (anionic surfactant, sodium alkylnaphthalene sulfonate, manufactured by Kao Corporation) Lapisol A-80 (anionic surfactant, sodium di (2-ethylhexyl) sulfosuccinate, manufactured by NOF Corporation)
- Coating method 1 As a coating device, a non-contact dispenser type AeroJet manufactured by Musashi Engineering Co., Ltd. was used. Under the conditions of a clearance of 6 mm and a discharge pressure of 0.05 MPa, the conveyance speed is adjusted so that the coating amount (solid content) is 0.8 g / m 2 , so that the edge of the planographic printing plate precursor is 0.3 cm. After the treatment liquid was applied, it was dried at 120 ° C. for 1 minute using a thermostat PH-201 manufactured by Espec Corp.
- Coating method 2 The cloth containing the treatment liquid is brought into contact with the edge of the lithographic printing plate precursor, and the coating method 1 is applied to an area of at least 0.5 cm from the edge of the lithographic printing plate precursor while sliding the cloth along the edge. After applying the treatment liquid so that the application amount was almost the same, it was dried at 120 ° C. for 1 minute using a thermostat PH-201 manufactured by ESPEC Corporation.
- Coating method 3 The cloth containing the above treatment liquid is brought into contact with the edge of the lithographic printing plate precursor, and the cloth is pressed from above and applied in the area of at least 0.5 cm from the edge of the lithographic printing plate precursor, approximately the same coating amount as in coating method 1.
- an on-press development type lithographic printing plate precursor that gives a lithographic printing plate that does not cause edge smearing, has no unexposed part in the vicinity of the edge part, and has a wide water width at the time of printing against edge smearing.
- a processing method and a printing method can be provided.
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- Manufacturing & Machinery (AREA)
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Abstract
Description
(2)前記塗布手段が、液体定量吐出装置である(1)に記載の処理方法。
(3)前記平版印刷版原版の端部が、ダレ量Xが35~150μm、ダレ幅Yが50~300μmのダレ形状を有する(1)又は(2)に記載の処理方法。
(4)前記親水化剤が、リン酸化合物、ホスホン酸化合物、アニオン性界面活性剤及び非イオン性界面活性剤から選択される少なくとも1つである(1)~(3)のいずれか1項に記載の処理方法。
(5)前記親水化剤が、リン酸化合物及びホスホン酸化合物から選択される少なくとも1つ並びにアニオン性界面活性剤及び非イオン性界面活性剤から選択される少なくとも1つである(4)に記載の処理方法。
(6)前記画像記録層が、赤外線吸収剤、重合開始剤、重合性化合物及びバインダーポリマーを含有する(1)~(5)のいずれか1項に記載の処理方法。
(7)前記画像記録層が、赤外線吸収剤、重合開始剤、重合性化合物及び微粒子形状の高分子化合物を含有する(1)~(5)のいずれか1項に記載の処理方法。
(8)前記画像記録層が、赤外線吸収剤及び熱可塑性微粒子ポリマーを含有する(1)~(5)のいずれか1項に記載の処理方法。
(9)(1)~(8)のいずれか1項に記載の処理方法で処理された平版印刷版原版を、印刷機のシリンダーに装着し、インキ及び湿し水を供給して機上現像した後印刷する印刷方法。
本発明に係る機上現像型平版印刷版原版の処理方法は、支持体上に画像記録層を有する機上現像型平版印刷版原版を画像露光した後、印刷機に装着する前に、平版印刷版原版の版面の端部から1cm以内の領域に親水化剤を含有する処理液を塗布する処理方法であって、前記塗布を、塗布手段が版面に接触しないように行う処理方法である。本発明の処理方法においては、平版印刷版原版の版面の端部領域に親水化剤を含有する処理液を塗布するに際して、塗布手段が版面に接触しないように行うことが特徴である。塗布手段が版面に接触すると、平版印刷版原版の画像記録層に物理的な力が加わり画像記録層が損傷して脱膜し、この脱膜成分がカスとなって版面に付着して非画像部の汚れを引き起こすと考えられるが、本発明の処理方法においてはこのような問題は発生しない。更に、本発明の処理方法によれば、塗布手段が版面に接触しないように塗布することにより、塗布手段を版面に接触させて塗布する場合と比較して、印刷時の湿し水量を少なくした場合でもエッジ汚れの発生が抑制させるという全く予想外の優れた効果が認められることが判明した。
初めに、本発明に係る処理方法に用いられる親水化剤を含有する処理液について説明する。
本発明の処理方法に用いられる親水化剤を含有する処理液は水溶液であってもよく、油相成分と水相成分を乳化した処理液(乳化型処理液)であってもよいが、水溶液であることが好ましい。
処理液に含まれる親水化剤は、リン酸化合物、ホスホン酸化合物、アニオン性界面活性剤及び非イオン性界面活性剤から選択される少なくとも1つであることが好ましい。親水化剤としては、リン酸化合物及びホスホン酸化合物が好ましい。
親水化剤は、リン酸化合物及びホスホン酸化合物から選択される少なくとも1つ並びにアニオン性界面活性剤及び非イオン性界面活性剤から選択される少なくとも1つであることがより好ましい。
親水化剤として用いられるリン酸化合物としては、リン酸、その塩が好ましく用いられ、例えば、リン酸、メタリン酸、第一リン酸アンモニウム、第二リン酸アンモニウム、第一リン酸ナトリウム、第二リン酸ナトリウム、第三リン酸ナトリウム、第一リン酸カリウム、第二リン酸カリウム、トリポリリン酸ナトリウム、ピロリン酸カリウム、ヘキサメタリン酸ナトリウムなどが挙げられる。また、リン酸/リン酸アンモニウム、リン酸/リン酸ナトリウム、メタリン酸/リン酸アンモニウムといった酸と塩の組み合わせが好ましく使用できる。
親水化剤として用いられるホスホン酸化合物としては、ホスホン酸、その塩、そのエステルが好ましく用いられ、例えば、エチルホスホン酸、プロピルホスホン酸、イソプロピルホスホン酸、ブチルホスホン酸、ヘキシルホスホン酸、オクチルホスホン酸、ドデシルホスホン酸、オクタデシルホスホン酸、2-ヒドロキシエチルホスホン酸及びこれらのナトリウム塩又はカリウム塩、ポリビニルホスホン酸、メチルホスホン酸メチル、エチルホスホン酸メチル、2-ヒドロキシエチルホスホン酸メチルなどのアルキルホスホン酸モノアルキルエステル及びこれらのナトリウム塩又はカリウム塩、メチレンジホスホン酸、エチレンジホスホン酸などのアルキレンジホスホン酸及びこれらのナトリウム塩又はカリウム塩などが挙げられる。
親水化剤として用いられるアニオン性界面活性剤としては、脂肪酸塩類、アビエチン酸塩類、ヒドロキシアルカンスルホン酸塩類、アルカンスルホン酸塩類、ジアルキルスルホコハク酸塩類、ベンゼンスルホン酸塩類、直鎖アルキルベンゼンスルホン酸塩類、分岐鎖アルキルベンゼンスルホン酸塩類、ナフタレンスルホン酸塩類、アルキルナフタレンスルホン酸塩類、アルキルフェノキシポリオキシエチレンプロピルスルホン酸塩類、ポリオキシエチレンアリールエーテル硫酸エステル塩類、ポリオキシエチレンアルキルスルホフェニルエーテル塩類、N-メチル-N-オレイルタウリンナトリウム類、N-アルキルスルホコハク酸モノアミド二ナトリウム塩類、石油スルホン酸塩類、硫酸化ヒマシ油、硫酸化牛脂油、脂肪酸アルキルエステルの硫酸エステル塩類、アルキル硫酸エステル塩類、ポリオキシエチレンアルキルエーテル硫酸エステル塩類、脂肪酸モノグリセリド硫酸エステル塩類、ポリオキシエチレンアルキルフェニルエーテル硫酸エステル塩類、ポリオキシエチレンスチリルフェニルエーテル硫酸エステル塩類、アルキル燐酸エステル塩類、ポリオキシエチレンアルキルエーテル燐酸エステル塩類、ポリオキシエチレンアルキルフェニルエーテル燐酸エステル塩類、スチレン-無水マレイン酸共重合物の部分ケン化物類、オレフィン-無水マレイン酸共重合物の部分ケン化物類、ナフタレンスルホン酸塩ホルマリン縮合物類等が挙げられる。なお、フッ素系及びシリコン系のアニオン性界面活性剤は本発明における親水化剤として用いられるアニオン性界面活性剤に該当しない。
一般式(I-B)中、R2は直鎖又は分岐鎖の炭素原子数1~20のアルキル基を表し、mは0、1又は2を表し、Ar2は炭素原子数6~10のアリール基を表し、Yは単結合又は炭素原子数1~10のアルキレン基を表し、R3は直鎖又は分岐鎖の炭素原子数1~5のアルキレン基を表し、nは1~100の整数を表し、M2 +は、Na+、K+、Li+又はNH4 +を表す。mが2の場合、複数存在するR2は互いに同じでも異なっていてもよく、nが2以上の場合、複数存在するR3は互いに同じでも異なっていてもよい。
親水化剤として用いられる非イオン性界面活性剤としては、ポリオキシエチレンアルキルエーテル類、ポリオキシエチレンアリールエーテル類、ポリオキシエチレンアルキルエステル類、グリセリン脂肪酸部分エステル類、ソルビタン脂肪酸部分エステル類、ペンタエリスリトール脂肪酸部分エステル類、プロピレングリコールモノ脂肪酸エステル類、ショ糖脂肪酸部分エステル類、ポリオキシエチレンソルビタン脂肪酸部分エステル類、ポリオキシエチレンソルビトール脂肪酸部分エステル類、ポリエチレングリコール脂肪酸エステル類、ポリグリセリン脂肪酸部分エステル類、ポリオキシエチレングリセリン脂肪酸部分エステル類、脂肪酸ジエタノールアミド類、N,N-ビス-2-ヒドロキシアルキルアミン類、ポリオキシエチレンアルキルアミン類、トリエタノールアミン脂肪酸エステル類、トリアルキルアミンオキシド類、ポリオキシエチレン-ポリオキシプロピレンブロック共重合体類などが挙げられる。なお、フッ素系及びシリコン系の非イオン性界面活性剤は本発明における親水化剤として用いられる非イオン性界面活性剤に該当しない。
水溶性樹脂は、粘度調整及び親水化保護膜形成によるエッジ汚れ防止効果の持続性の目的で含有させることができる。水溶性樹脂としては、多糖類として分類される水溶性樹脂、ポリビニルアルコール、ポリビニルピロリドン、ポリアクリルアミド及びその共重合体、ビニルメチルエーテル/無水マレイン酸共重合体、酢酸ビニル/無水マレイン酸共重合体、スチレン/無水マレイン酸共重合体等が挙げられる。
水溶性樹脂の中で、デキストリン、ポリオキシアルキレングラフト化澱粉等の澱粉誘導体、アラビアガム、カルボキシメチルセルロース、大豆多糖類等が好ましく用いられる。
有機溶剤は、親水化剤、水溶性樹脂の溶解度調整、画像記録層の膨潤を促進する目的で含有させることができる。有機溶剤としては、アルコール系溶剤、ケトン系溶剤、エステル系溶剤、アミド系溶剤、炭化水素系溶剤等が挙げられる。有機溶剤の中で、アルコール系溶剤及び炭化水素系溶剤が好ましく用いられる。
多価アルコールとしては、エチレングリコール、プロピレングリコール、トリエチレングリコール、ブチレングリコール、ヘキシレングリコール、ジエチレングリコール、ジプロピレングリコール、グリセリン等が挙げられる。
好ましくは、ベンジルアルコール、フェネチルアルコール、フルフリルアルコール、グリセリンである。
可塑剤としては、ジブチルフタレート、ジヘプチルフタレート、ジ-n-オクチルフタレート、ジ(2-エチルヘキシル)フタレート、ジノニルフタレート、ジデシルフタレート、ジラウリルフタレート、ブチルベンジルフタレートなどのフタル酸ジエステル類、ジオクチルアジペート、ブチルグリコールアジペート、ジオクチルアゼレート、ジブチルセバケート、ジ(2-エチルヘキシル)セバケート、ジオクチルセバケートなどの脂肪族二塩基酸エステル類、エポキシ化大豆油などのエポキシ化トリグリセリド類、トリクレジルフォスフェート、トリオクチルフォスフェート、トリスクロルエチルフォスフェートなどの燐酸エステル類、安息香酸ベンジルなどの安息香酸エステル類などの凝固点が15℃以下の可塑剤が含まれる。
親水化剤を含有する処理液は、上記の他に、硝酸塩、硫酸塩などの無機塩、防腐剤、消泡剤等を含有してもよい。
無機塩としては、硝酸マグネシウム、硝酸ナトリウム、硝酸カリウム、硝酸アンモニウム、硫酸ナトリウム、硫酸カリウム、硫酸アンモニウム、硫酸水素ナトリウム、硫酸ニッケル等が挙げられる。
防腐剤としては、フェノール又はその誘導体、ホルマリン、イミダゾール誘導体、デヒドロ酢酸ナトリウム、4-イソチアゾリン-3-オン誘導体、ベンゾイソチアゾリン-3-オン、ベンズトリアゾール誘導体、アミジングアニジン誘導体、四級アンモニウム塩類、ピリジン、キノリン、グアニジン等の誘導体、ダイアジン、トリアゾール誘導体、オキサゾール、オキサジン誘導体、ニトロブロモアルコール系の2-ブロモ-2-ニトロプロパン-1,3ジオール、1,1-ジブロモ-1-ニトロ-2-エタノール、1,1-ジブロモ-1-ニトロ-2-プロパノール等が挙げられる。
消泡剤としては一般的なシリコン系の自己乳化タイプ、乳化タイプ、HLB5以下のノニオン性界面活性剤を使用することができる。
親水化剤を含有する処理液は、カチオン性界面活性剤や両性界面活性剤を含有してもよい。カチオン性界面活性剤としては、例えば、アルキルアミン塩類、第4級アンモニウム塩類、ポリオキシアルキルアミン塩類、ポリエチレンポリアミン誘導体などが挙げられる。両性界面活性剤としては、例えば、カルボキシベタイン類、アミノカルボン酸類、スルホベタイン類、アミノ硫酸エステル類、イミダゾリン類などが挙げられる。
親水化剤を含有する処理液は、常法に従って調製することができる。処理液が水溶液である場合には、親水化剤及び必要によりその他の成分を水(蒸留水、イオン交換水、脱塩水など)に溶解して調製される。
乳化型処理液である場合も、常法に従って調製することができる。処理液を調製する際の乳化分散は、例えば、親水化剤を含む水相を温度40℃±5℃に調製し、高速攪拌しながら、水相中に別途調製した有機溶剤からなる油相をゆっくり滴下し充分攪拌後、圧力式のホモジナイザーを通して乳化液とする方法で行うことができる。
親水化剤を含有する処理液は、先ず濃縮した形態で調製し、使用時に適宜希釈することもある。
親水化剤を含有する処理液による平版印刷版原版の処理方法について説明する。本発明に係る処理方法によれば、画像露光された機上現像型平版印刷版原版の版面の端部から1cm以内の領域に、親水化剤を含有する処理液を塗布手段が版面に接触しないように塗布する。平版印刷版原版の版面とは、平版印刷版原版の画像記録層を有する側の表面を意味し、通常、画像記録層表面又は画像記録層上に設けられる保護層表面である。端部とは、平版印刷版原版の製造過程において、シート状に裁断する工程などにより形成さる縁の部分を指す。
端部領域に塗布される処理液の塗布量は、乾燥後の固形分として、0.05~3g/m2が好ましく、0.1~2g/m2がより好ましい。この範囲が、塗布部分のべた付きによる平版印刷版原版同士の接着防止、機上現像性への影響の観点から好ましい。
これに対して、特開2011-177983号公報に記載のように、処理液を含ませた布やモルトンロール等を用いる塗布は、塗布手段が平版印刷版原版の版面に接触するため、本発明に係る処理液を塗布手段が版面に接触しないように塗布することに該当しない。
ディスペンサー方式としては、エアー圧縮方式、バルブ開閉方式、ピストン方式、チューブ方式、スクリュー吐出方式を用いることができる。
本発明の処理方法に用いられる機上現像型平版印刷版原版(以下、単に、平版印刷版原版ということもある)は、支持体上に画像記録層を有する。平版印刷版原版は、必要により、支持体と画像記録層との間に下塗り層(中間層ということもある)、画像記録層の上に保護層(オーバーコート層ということもある)を有してもよい。
平版印刷版原版の画像記録層は、その非画像部が、印刷機上で中性~アルカリ性の湿し水及び印刷インキの少なくとも1方により除去される画像記録層である。
本発明の1つの態様によれば、画像記録層は、赤外線吸収剤、重合開始剤、重合性化合物及びバインダーポリマーを含有する画像記録層(以下、画像記録層Aともいう)である。
本発明のもう1つの態様によれば、画像記録層は、赤外線吸収剤、重合開始剤、重合性化合物及び微粒子形状の高分子化合物を含有する画像記録層(以下、画像記録層Bともいう)である。
本発明の更にもう1つの態様によれば、画像記録層は、赤外線吸収剤及び熱可塑性微粒子ポリマーを含有する画像記録層(以下、画像記録層Cともいう)である。
画像記録層Aは、赤外線吸収剤、重合開始剤、重合性化合物及びバインダーポリマーを含有する。以下、画像記録層Aの構成成分について説明する。
赤外線吸収剤は、吸収した赤外線を熱に変換する機能と赤外線により励起して後述の重合開始剤に電子移動及び/又はエネルギー移動する機能を有する。本発明において使用される赤外線吸収剤は、波長760~1200nmに吸収極大を有する染料又は顔料が好ましく、染料がより好ましい。
これらの染料のうち特に好ましいものとしては、シアニン色素、スクアリリウム色素、ピリリウム塩、ニッケルチオレート錯体、インドレニンシアニン色素が挙げられる。更に、シアニン色素やインドレニンシアニン色素が好ましく、特に好ましい例として下記一般式(a)で示されるシアニン色素が挙げられる。
また特開平5-5005号公報の段落番号[0008]~[0009]、特開2001-222101号公報の段落番号[0022]~[0025]に記載の化合物も好ましく使用することが出来る。
赤外線吸収剤の含有量は、画像記録層の全固形分100質量部に対し、好ましくは0.05~30質量部、より好ましくは0.1~20質量部、特に好ましくは0.2~10質量部である。
重合開始剤は、重合性化合物の重合を開始、促進する化合物である。重合開始剤としては、公知の熱重合開始剤、結合解離エネルギーの小さな結合を有する化合物、光重合開始剤などを使用することができる。
(g)ヘキサアリールビイミダゾール化合物としては、例えば、特開2008-195018号公報の段落番号[0027]に記載の化合物が好ましい。
重合性化合物は、少なくとも一個のエチレン性不飽和二重結合を有する付加重合性化合物であり、末端エチレン性不飽和結合を少なくとも1個、好ましくは2個以上有する化合物から選ばれる。これらは、例えばモノマー、プレポリマー、すなわち2量体、3量体及びオリゴマー、又はそれらの混合物などの化学的形態を有する。
CH2=C(R4)COOCH2CH(R5)OH (b)
(ただし、R4及びR5は、H又はCH3を示す。)
バインダーポリマーは、主として画像記録層の膜強度を向上させる目的で用いられる。バインダーポリマーは、従来公知のものを使用でき、皮膜性を有するポリマーが好ましい。なかでも、アクリル樹脂、ポリビニルアセタール樹脂、ポリウレタン樹脂などが好ましい。
また、「パーフルオロアルキル基」とは、アルキル基の全ての水素原子がフッ素原子で置換され基である。
ポリオキシアルキレン鎖、すなわち、ポリ(アルキレンオキサイド)部位におけるアルキレンオキサイドの繰返し数は2~50が好ましく、4~25がより好ましい。
アルキレンオキサイドの繰り返し数が2以上であれば湿し水の浸透性が十分向上し、また、繰り返し数が50以下であれば摩耗による耐刷性が低下することがなく、好ましい。
一般式(1)において、R1は水素原子又はメチル基が好ましく、水素原子が特に好ましい。R2は水素原子又はメチル基が特に好ましい。
分子の主鎖中にエチレン性不飽和結合を有する高分子化合物の例としては、ポリ-1,4-ブタジエン、ポリ-1,4-イソプレンなどが挙げられる。
分子の側鎖中にエチレン性不飽和結合を有する高分子化合物の例としては、アクリル酸又はメタクリル酸のエステル若しくはアミドの高分子化合物であって、エステル又はアミドの残基(-COOR又はCONHRのR)がエチレン性不飽和結合を有する高分子化合物を挙げることができる。
アミド残基の具体例としては、-CH2CH=CH2、-CH2CH2-Y(式中、Yはシクロヘキセン残基を表す。)、-CH2CH2-OCO-CH=CH2が挙げられる。
R22の好ましい例としては、エステル基、アミド基、シアノ基、ヒドロキシ基、又はアリール基が挙げられる。なかでも、エステル基、アミド基、又は置換基を有してよいフェニル基が好ましい。フェニル基の置換基としては、アルキル基、アラルキル基、アルコキシ基、アセトキシメチル基などが挙げられる。
重合性基としては、(メタ)アクリル基、ビニル基、アリル基、スチリル基などのエチレン性不飽和基やエポキシ基等が好ましく、(メタ)アクリル基、ビニル基、スチリル基が重合反応性の観点でより好ましく、(メタ)アクリル基が特に好ましい。これらの基は高分子反応や共重合によってポリマーに導入することができる。例えば、カルボキシ基を側鎖に有するポリマーとグリシジルメタクリレートとの反応、あるいはエポキシ基を有するポリマーとメタクリル酸などのエチレン性不飽和基含有カルボン酸との反応を利用できる。これらの基は併用してもよい。
星型高分子化合物の含有率は、画像記録層の全固形分に対し、5~95質量%が好ましく、10~90質量%以下がより好ましく、15~85質量%以下が特に好ましい。
特に、湿し水の浸透性が促進され、機上現像性が向上することから、特開2012-148555号公報に記載の星型高分子化合物が好ましい。
画像記録層Aには、必要に応じて、以下に記載するその他の成分を含有させることができる。
画像記録層は、耐刷性を低下させることなく機上現像性を向上させるために、低分子親水性化合物を含有してもよい。
低分子親水性化合物としては、例えば、水溶性有機化合物としては、エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、ジプロピレングリコール、トリプロピレングリコール等のグリコール類及びそのエーテル又はエステル誘導体類、グリセリン、ペンタエリスリトール、トリス(2-ヒドロキシエチル)イソシアヌレート等のポリオール類、トリエタノールアミン、ジエタノールアミン、モノエタノールアミン等の有機アミン類及びその塩、アルキルスルホン酸、トルエンスルホン酸、ベンゼンスルホン酸等の有機スルホン酸類及びその塩、アルキルスルファミン酸等の有機スルファミン酸類及びその塩、アルキル硫酸、アルキルエーテル硫酸等の有機硫酸類及びその塩、フェニルホスホン酸等の有機ホスホン酸類及びその塩、酒石酸、シュウ酸、クエン酸、リンゴ酸、乳酸、グルコン酸、アミノ酸類等の有機カルボン酸類及びその塩、ベタイン類、等が挙げられる。
化合物は単独で用いてもよく、2種以上を混合して用いてもよい。
画像記録層には、着肉性を向上させるために、ホスホニウム化合物、含窒素低分子化合物、アンモニウム基含有ポリマーなどの感脂化剤を用いることができる。特に、保護層に無機質層状化合物を含有させる場合には、これらの化合物は、無機質層状化合物の表面被覆剤として機能し、無機質層状化合物による印刷途中の着肉性低下を防止する作用を有する。
30質量%ポリマー溶液3.33g(固形分として1g)を、20mlのメスフラスコに秤量し、N-メチルピロリドンでメスアップする。この溶液を30℃の恒温槽で30分間静置し、ウベローデ還元粘度管(粘度計定数=0.010cSt/s)に入れて30℃にて流れ落ちる時間を測定する。なお測定は同一サンプルで2回測定し、その平均値を算出する。同様にブランク(N-メチルピロリドンのみ)の場合も測定し、下記式から還元比粘度(ml/g)を算出する。
(1)2-(トリメチルアンモニオ)エチルメタクリレート=p-トルエンスルホナート/3,6-ジオキサヘプチルメタクリレート共重合体(モル比10/90 Mw4.5万)(2)2-(トリメチルアンモニオ)エチルメタクリレート=ヘキサフルオロホスファート/3,6-ジオキサヘプチルメタクリレート共重合体(モル比20/80 Mw6.0万)(3)2-(エチルジメチルアンモニオ)エチルメタクリレート=p-トルエンスルホナート/ヘキシルメタクリレート共重合体(モル比30/70 Mw4.5万)(4)2-(トリメチルアンモニオ)エチルメタクリレート=ヘキサフルオロホスファート/2-エチルヘキシルメタクリレート共重合体(モル比20/80 Mw6.0万)(5)2-(トリメチルアンモニオ)エチルメタクリレート=メチルスルファート/ヘキシルメタクリレート共重合体(モル比40/60 Mw7.0万)(6)2-(ブチルジメチルアンモニオ)エチルメタクリレート=ヘキサフルオロホスファート/3,6-ジオキサヘプチルメタクリレート共重合体(モル比 25/75 Mw6.5万)(7)2-(ブチルジメチルアンモニオ)エチルアクリレート=ヘキサフルオロホスファート/3,6-ジオキサヘプチルメタクリレート共重合体(モル比20/80 Mw6.5万)(8)2-(ブチルジメチルアンモニオ)エチルメタクリレート=13-エチル-5,8,11-トリオキサ-1-ヘプタデカンスルホナート/3,6-ジオキサヘプチルメタクリレート共重合体(モル比20/80 Mw7.5万)(9)2-(ブチルジメチルアンモニオ)エチルメタクリレート=ヘキサフルオロホスファート/3,6-ジオキサヘプチルメタクリレート/2-ヒドロキシ-3-メタクロイルオキシプロピルメタクリレート共重合体(モル比15/80/5 Mw6.5万)
画像記録層は、その他の成分として、更に、界面活性剤、着色剤、焼き出し剤、重合禁止剤、高級脂肪酸誘導体、可塑剤、無機微粒子、無機質層状化合物、共増感剤、連鎖移動剤などを含有することができる。具体的には、特開2008-284817号公報の段落番号[0114]~[0159]、特開2006-091479号公報の段落番号[0023]~[0027]、米国特許公開2008/0311520号明細書の段落番号[0060]に記載の化合物及び添加量を好ましく用いることができる。
画像記録層は、例えば、特開2008-195018号公報の段落番号[0142]~[0143]に記載のように、必要な上記各成分を公知の溶剤に分散又は溶解して塗布液を調製し、これを支持体上にバーコーター塗布など公知の方法で塗布し、乾燥することで形成される。塗布、乾燥後に得られる支持体上の画像記録層塗布量(固形分)は、用途によって異なるが、通常0.3~3.0g/m2が好ましい。この範囲で、良好な感度と画像記録層の良好な皮膜特性が得られる。
画像記録層Bは、赤外線吸収剤、重合開始剤、重合性化合物及び微粒子形状の高分子化合物を含有する。以下、画像記録層Bの構成成分について説明する。
微粒子形状の高分子化合物は、疎水性熱可塑性ポリマー微粒子、熱反応性ポリマー微粒子、重合性基を有するポリマー微粒子、疎水性化合物を内包しているマイクロカプセル、及びミクロゲル(架橋ポリマー微粒子)から選ばれることが好ましい。なかでも、重合性基を有するポリマー微粒子及びミクロゲルが好ましい。特に好ましい実施形態では、微粒子形状の高分子化合物は少なくとも1つのエチレン性不飽和重合性基を含む。このような微粒子形状の高分子化合物の存在により、露光部の耐刷性及び未露光部の機上現像性を高める効果が得られる。
疎水性熱可塑性ポリマー微粒子を構成するポリマーの具体例としては、エチレン、スチレン、塩化ビニル、アクリル酸メチル、アクリル酸エチル、メタクリル酸メチル、メタクリル酸エチル、塩化ビニリデン、アクリロニトリル、ビニルカルバゾール、ポリアルキレン構造を有するアクリレート又はメタクリレートなどのモノマーのホモポリマー若しくはコポリマー又はそれらの混合物を挙げることができる。好ましくは、ポリスチレン、スチレン及びアクリロニトリルを含む共重合体、ポリメタクリル酸メチルを挙げることができる。疎水性熱可塑性ポリマー微粒子の平均粒径は0.01~3.0μmが好ましい。
画像記録層Bには、必要に応じて、前記画像記録層Aにおいて記載したその他の成分を含有させることができる。
画像記録層Bの形成に関しては、前記画像記録層Aの形成の記載を適用することができる。
画像記録層Cは、赤外線吸収剤及び熱可塑性微粒子ポリマーを含有する。以下、画像記録層Cの構成成分について説明する。
画像記録層Cに含まれる赤外線吸収剤は、好ましくは760~1200nm吸収極大を有する染料又は顔料である。染料がより好ましい。
以下に赤外線吸収染料の具体例を示すが、本発明はこれらに限定されるものではない。
熱可塑性微粒子ポリマーはそのガラス転移温度(Tg)が60℃~250℃であることが好ましい。熱可塑性微粒子ポリマーのTgは、70℃~140℃がより好ましく、80℃~120℃が更に好ましい。
Tgが60℃以上の熱可塑性微粒子ポリマーとしては、例えば、1992年1月のReseach Disclosure No.33303、特開平9-123387号公報、同9-131850号公報、同9-171249号公報、同9-171250号公報及びEP931647号公報などに記載の熱可塑性微粒子ポリマーを好適なものとして挙げることができる。
具体的には、エチレン、スチレン、塩化ビニル、アクリル酸メチル、アクリル酸エチル、メタクリル酸メチル、メタクリル酸エチル、塩化ビニリデン、アクリロニトリル、ビニルカルバゾールなどのモノマーから構成されるホモポリマー若しくはコポリマー又はそれらの混合物などを例示することができる。好ましいものとして、ポリスチレン、ポリメタクリル酸メチルなどが挙げられる。
例えば、熱可塑性微粒子ポリマーとして粒子サイズが同じものを用いた場合には、熱可塑性微粒子ポリマー間にある程度の空隙が存在することになり、画像露光により熱可塑性微粒子ポリマーを溶融固化させても皮膜の硬化性が所望のものにならないことがある。これに対して、熱可塑性微粒子ポリマーとして粒子サイズが異なるものを用いた場合、熱可塑性微粒子ポリマー間にある空隙率を低くすることができ、その結果、画像露光後の画像部の皮膜硬化性を向上させることができる。
架橋性基の導入を微粒子ポリマーの重合後に行う場合に用いる高分子反応としては、例えば、WO96/34316号に記載されている高分子反応を挙げることができる。
熱可塑性微粒子ポリマーは、架橋性基を介して微粒子ポリマー同士が反応してもよいし、画像記録層に添加された高分子化合物あるいは低分子化合物と反応してもよい。
画像記録層Cは、必要に応じて、更にその他の成分を含有してもよい。
ポリオキシアルキレン基(以下、POA基とも記載する)又はヒドロキシ基を有する界面活性剤としては、POA基又はヒドロキシ基を有する界面活性剤を適宜用いることができるが、アニオン界面活性剤又はノニオン界面活性剤が好ましい。POA基又はヒドロキシ基を有するアニオン界面活性剤又はノニオン界面活性剤の中で、POA基を有するアニオン界面活性剤又はノニオン界面活性剤が好ましい。
オキシアルキレン基の平均重合度は通常2~50が適当であり、好ましくは2~20である。
ヒドロキシ基の数は通常1~10が適当であり、好ましくは2~8である。但し、オキシアルキレン基における末端ヒドロキシ基は、ヒドロキシ基の数には含めない。
POA基を有するアニオン界面活性剤としては、特に限定されず、ポリオキシアルキレンアルキルエーテルカルボン酸塩類、ポリオキシアルキレンアルキルスルホコハク酸塩類、ポリオキシアルキレンアルキルエーテル硫酸エステル塩類、アルキルフェノキシポリオキシアルキレンプロピルスルホン酸塩類、ポリオキシアルキレンアルキルスルホフェニルエーテル類、ポリオキシアルキレンアリールエーテル硫酸エステル塩類、ポリオキシアルキレン多環フェニルエーテル硫酸エステル塩類、ポリオキシアルキレンスチリルフェニルエーテル硫酸エステル塩類、ポリオキシアルキレンルキルエーテル燐酸エステル塩類、ポリオキシアルキレンアルキルフェニルエーテル燐酸エステル塩類、ポリオキシアルキレンパーフルオロアルキルエーテル燐酸エステル塩類等が挙げられる。
ヒドロキシ基を有するアニオン界面活性剤としては、特に限定されず、ヒドロキシカルボン酸塩類、ヒドロキシアルキルエーテルカルボン酸塩類、ヒドロキシアルカンスルホン酸塩類、脂肪酸モノグリセリド硫酸エステル塩類、脂肪酸モノグリセリドリン酸エステル塩類等が挙げられる。
当該アニオン界面活性剤は、上記目的を達成する限り、特に制限されない。中でも、アルキルベンゼンスルホン酸又はその塩、アルキルナフタレンスルホン酸又はその塩、(ジ)アルキルジフェニルエーテル(ジ)スルホン酸又はその塩、アルキル硫酸エステル塩が好ましい。
無機微粒子の含有量は、画像記録層固形分の1.0~70質量%が好ましく、5.0~50質量%がより好ましい。
可塑剤の含有量は、画像記録層固形分の0.1%~50質量%が好ましく、1~30質量%がより好ましい。
画像記録層は、必要な上記各成分を適当な溶剤に溶解又は分散して塗布液を調製し、支持体に塗布して形成される。溶剤としては、水又は水と有機溶剤との混合溶剤が用いられるが、水と有機溶剤の混合使用が、塗布後の面状を良好にする点で好ましい。有機溶剤の量は、有機溶剤の種類によって異なるので、一概に特定できないが、通常混合溶剤中5~50容量%が好ましい。但し、有機溶剤は熱可塑性微粒子ポリマーが凝集しない範囲の量で使用する必要がある。画像記録層用塗布液の固形分濃度は、好ましくは1~50質量%である。
平版印刷版原版は、画像記録層と支持体との間に下塗り層(中間層と呼ばれることもある)を設けることが好ましい。下塗り層は、露光部においては支持体と画像記録層との密着を強化し、未露光部においては画像記録層の支持体からのはく離を生じやすくさせるため、耐刷性を損なわず機上現像性を向上させるのに寄与する。また、赤外線レーザー露光の場合は、下塗り層が断熱層として機能することにより、露光により発生した熱が支持体に拡散して感度が低下するのを防ぐ作用を有する。
下塗り層用高分子化合物は、質量平均モル質量が5000以上であるのが好ましく、1万~30万であるのがより好ましい。
平版印刷版原版の支持体としては、公知の支持体が用いられる。なかでも、公知の方法で粗面化処理され、陽極酸化処理されたアルミニウム板が好ましい。
アルミニウム板には、必要に応じて、特開2001-253181号公報や特開2001-322365号公報に記載されている陽極酸化皮膜のマイクロポアの拡大処理や封孔処理、及び米国特許第2,714,066号、同第3,181,461号、同第3,280,734号及び同第3,902,734号の各明細書に記載されているようなアルカリ金属シリケートあるいは米国特許第3,276,868号、同第4,153,461号及び同第4,689,272号の各明細書に記載されているようなポリビニルホスホン酸などによる表面親水化処理を適宜選択して行うことができる。
支持体は、中心線平均粗さが0.10~1.2μmであることが好ましい。
平版印刷版原版は、画像記録層の上に保護層(オーバーコート層)を設けることが好ましい。保護層は酸素遮断によって画像形成阻害反応を抑制する機能の他、画像記録層における傷の発生防止、及び高照度レーザー露光時のアブレーション防止の機能を有する。
変性ポリビニルアルコールとしては、カルボキシ基又はスルホ基を有する酸変性ポリビニルアルコールが好ましく用いられる。具体的には、特開2005-250216号、特開2006-259137号の公報に記載の変性ポリビニルアルコールが好ましい。
なかでもデキストリン、ポリオキシアルキレングラフト化澱粉といった澱粉誘導体、アラビアガム、カルボキシメチルセルロース、大豆多糖類などが好ましく用いられる。
多糖類は、保護層の固形分に対して、1~20質量%の範囲で使用することが好ましい。
更に、保護層は、可撓性付与のための可塑剤、塗布性を向上させための界面活性剤、表面の滑り性を制御するための無機微粒子など公知の添加物を含むことができる。また、画像記録層の説明に記載した感脂化剤を保護層に含有させることもできる。
本発明に係る処理方法に用いられる平版印刷版原版は、その端部がダレ形状を有していることが好ましい。端部にダレ形状を有する平版印刷版原版の使用は、本発明に係る処理方法と相まってエッジ汚れを防止するために有用である。
図1において、平版印刷版原版1はその端部にダレ2を有している。平版印刷版原版1の端面1cの上端(ダレ2と端面1cとの境界点)と、画像記録層面(保護層が形成されている場合には保護層面)1aの延長線との距離Xを「ダレ量」といい、平版印刷版原版1の画像記録層面1aがダレ始める点と端面1cの延長線上との距離Yを「ダレ幅」という。平版印刷版原版における端部のダレ量は35μm以上が好ましい。ダレ量の上限は150μmが好ましい。ダレ量が150μmを超えると、端部表面状態が著しく悪化し、機上現像性が劣化する。ダレ量の範囲が35~150μmの場合、ダレ幅が小さいと、端部にクラックが入り、そこに印刷インキが溜まることにより汚れが発生する原因となる。このようなクラックの発生を減らすため、ダレ幅は50~300μmの範囲が適当であり、70~250μmの範囲が好ましい。なお、上記ダレ量とダレ幅の好ましい範囲は、平版印刷版原版1の支持体面1bのエッジ形状には関わらない。
通常、平版印刷版原版1の端部において、画像記録層と支持体との境界B、及び、支持体面1bも、画像記録層面1aと同様に、ダレが発生している。
具体的には、平版印刷版原版の裁断時に使用するスリッター装置における上側裁断刃と下側裁断刃の隙間、噛み込み量、刃先角度などの調整により行うことができる。
例えば、図2は、スリッター装置の裁断部を示す断面図である。スリッター装置には、上下一対の裁断刃10、20が左右に配置されている。裁断刃10、20は円板上の丸刃からなり、上側裁断刃10a及び10bは回転軸11に、下側裁断刃20a及び20bは回転軸21に、それぞれ同軸上に支持されている。上側裁断刃10a及び10bと下側裁断刃20a及び20bとは、相反する方向に回転される。平版印刷版原版30は、上側裁断刃10a、10bと下側裁断刃20a,20bとの間を通されて所定の幅に裁断される。スリッター装置の裁断部の上側裁断刃10aと下側裁断刃20aとの隙間及び上側裁断刃10bと下側裁断刃20bとの隙間を調整することによりダレを有する端部を形成することができる。
本発明に係る処理方法における機上現像型平版印刷版原版の画像露光は、通常の機上現像型平版印刷版原版の画像露光操作に準じて行うことができる。
親水化剤を含有する処理液が端部領域に塗布された平版印刷版原版の機上現像及び印刷は、常法により行うことができる。即ち、親水化剤を含有する処理液が端部領域に塗布された平版印刷版原版を印刷機の版胴(シリンダー)に装着し、湿し水と印刷インキとを供給すると、画像記録層の露光部においては、露光により硬化した画像記録層が、親油性表面を有する印刷インキ受容部を形成する。一方、未露光部においては、供給された湿し水及び/又は印刷インキによって、未硬化の画像記録層が溶解又は分散して除去され、その部分に親水性の表面が露出する。その結果、湿し水は露出した親水性の表面に付着し、印刷インキは露光領域の画像記録層に着肉して印刷が開始される。
ここで、最初に平版印刷版原版の表面に供給されるのは、湿し水でもよく印刷インキでもよいが、湿し水を浸透させ機上現像性を促進するために、最初に湿し水を供給するのが好ましい。
(1)支持体の作製
厚み0.3mmのアルミニウム板(材質JIS A 1050)の表面の圧延油を除去するため、10質量%アルミン酸ソーダ水溶液を用いて50℃で30秒間、脱脂処理を施した後、毛径0.3mmの束植ナイロンブラシ3本とメジアン径25μmのパミス-水懸濁液(比重1.1g/cm3)を用いアルミニウム表面を砂目立てして、水でよく洗浄した。このアルミニウム板を45℃の25質量%水酸化ナトリウム水溶液に9秒間浸漬してエッチングを行い、水洗後、更に60℃で20質量%硝酸水溶液に20秒間浸漬し、水洗した。この時の砂目立て表面のエッチング量は約3g/m2であった。
次に、この板に15質量%硫酸水溶液(アルミニウムイオンを0.5質量%含む)を電解液として電流密度15A/dm2で2.5g/m2の直流陽極酸化皮膜を設けた後、水洗、乾燥して支持体(1)を作製した。
その後、非画像部の親水性を確保するため、支持体(1)に2.5質量%3号ケイ酸ソーダ水溶液を用いて60℃で10秒間、シリケート処理を施し、その後、水洗して支持体(2)を得た。Siの付着量は10mg/m2であった。支持体(2)の中心線平均粗さ(Ra)を直径2μmの針を用いて測定したところ、0.51μmであった。
次に、上記支持体(2)上に、下記組成の下塗り層用塗布液(1)を乾燥塗布量が20mg/m2になるよう塗布して、下塗り層を有する支持体を作製した。
・下記構造の下塗り層用化合物(1) 0.18g
・ヒドロキシエチルイミノ二酢酸 0.10g
・メタノール 55.24g
・水 6.15g
上記のようにして形成された下塗り層上に、下記組成の画像記録層塗布液(1)をバー塗布した後、100℃60秒でオーブン乾燥し、乾燥塗布量1.0g/m2の画像記録層を形成した。
画像記録層塗布液(1)は下記感光液(1)及びミクロゲル液(1)を塗布直前に混合し攪拌することにより調製した。
・高分子化合物(バインダーポリマー(1))〔下記構造〕0.240g
・赤外線吸収剤(1)〔下記構造〕 0.030g
・ボレート化合物 0.010g
テトラフェニルホウ酸ナトリウム
・重合開始剤(1)〔下記構造〕 0.162g
・重合性化合物 0.192g
トリス(アクリロイルオキシエチル)イソシアヌレート
(NKエステルA-9300、新中村化学(株)製)
・アニオン界面活性剤1〔下記構造〕 0.050g
・感脂化剤 0.055g
ホスホニウム化合物(1)〔下記構造〕
・感脂化剤 0.018g
ベンジル-ジメチル-オクチルアンモニウム・PF6塩
・感脂化剤 0.040g
アンモニウム基含有ポリマー〔下記構造〕
・フッ素系界面活性剤(1)〔下記構造〕 0.008g
・2-ブタノン 1.091g
・1-メトキシ-2-プロパノール 8.609g
・ミクロゲル(1) 2.640g
・蒸留水 2.425g
油相成分として、トリメチロールプロパンとキシレンジイソシアナート付加体(三井化学ポリウレタン(株)製、タケネートD-110N)10g、ペンタエリスリトールトリアクリレート(日本化薬(株)製、SR444)3.15g、及びパイオニンA-41C(竹本油脂(株)製)0.1gを酢酸エチル17gに溶解した。水相成分としてポリビニルアルコール(PVA-205、(株)クラレ製)の4質量%水溶液40gを調製した。油相成分及び水相成分を混合し、ホモジナイザーを用いて12,000rpmで10分間乳化した。得られた乳化物を、蒸留水25gに添加し、室温で30分攪拌後、50℃で3時間攪拌した。このようにして得られたミクロゲル液の固形分濃度を、15質量%になるように蒸留水を用いて希釈してミクロゲル(1)を調製した。ミクロゲルの平均粒径を光散乱法により測定したところ、0.2μmであった。
上記画像記録層上に、下記組成の保護層塗布液(1)をバー塗布した後、120℃、60秒でオーブン乾燥し、乾燥塗布量0.15g/m2の保護層を形成して平版印刷版原版Iを作製した。
・無機質層状化合物分散液(1) 1.5g
・親水性ポリマー(1)(固形分)〔下記構造、Mw:3万〕 0.55g
・ポリビニルアルコール(日本合成化学工業(株)製CKS50、
スルホン酸変性、けん化度99モル%以上、重合度300)
6質量%水溶液 0.10g
・ポリビニルアルコール((株)クラレ製PVA-405、
けん化度81.5モル%、重合度500)6質量%水溶液 0.03g
・界面活性剤(エマレックス710、商品名:日本エマルジョン(株)製)
1質量%水溶液 0.86g
・イオン交換水 6.0g
イオン交換水193.6gに合成雲母ソマシフME-100(コープケミカル(株)製)6.4gを添加し、ホモジナイザーを用いて平均粒径(レーザー散乱法)が3μmになるまで分散した。得られた分散粒子のアスペクト比は100以上であった。
(支持体の作製)
厚さ0.19mmのアルミニウム板を40g/lの水酸化ナトリウム水溶液中に60℃で8秒間浸漬することにより脱脂し、脱塩水により2秒間洗浄した。次に、アルミニウム板を15秒間交流を用いて12g/lの塩酸及び38g/lの硫酸アルミニウム(18水和物)を含有する水溶液中で、33℃の温度及び130A/dm2の電流密度で電気化学的粗面化処理を行った。脱塩水により2秒間洗浄した後、アルミニウム板を155g/lの硫酸水溶液により70℃で4秒間エッチングすることによりデスマット処理し、脱塩水により25℃で2秒間洗浄した。アルミニウム板を13秒間155g/lの硫酸水溶液中で、45℃の温度及び22A/dm2の電流密度で陽極酸化処理し、脱塩水で2秒間洗浄した。更に、4g/lのポリビニルホスホン酸水溶液を用いて40℃で10秒間処理し、脱塩水により20℃で2秒間洗浄し、乾燥した。このようにして得られた支持体は、表面粗さRaが0.21μmで、陽極酸化皮膜量は4g/m2であった。
下記熱可塑性微粒子ポリマー、赤外線吸収剤及びポリアクリル酸を含有する画像記録層用水系塗布液を調製し、pHを3.6に調整した後、上記支持体上に塗布し、50℃で1分間乾燥して画像記録層を形成して平版印刷版原版IIを作製した。各成分の乾燥後の塗布量を以下に示す。
赤外線吸収剤 IR-01: 0.104g/m2
ポリアクリル酸: 0.09g/m2
赤外線吸収剤IR-01:下記構造の赤外線吸収剤
(1)画像記録層の形成
平版印刷版原版Iの作製に用いた下塗り層を有する支持体に、下記組成の画像記録層塗布液(2)をバー塗布した後、70℃、60秒でオーブン乾燥し、乾燥塗布量0.6g/m2の画像記録層を形成して平版印刷版原版IIIを作製した。
・高分子化合物微粒子水分散液(1) 20.0g
・赤外線吸収染料(2)〔下記構造〕 0.2g
・重合開始剤 Irgacure250
(チバスペシャリティケミカルズ製) 0.5g
・重合性化合物 SR-399(サートマー社製) 1.50g
・メルカプト-3-トリアゾール 0.2g
・Byk336(Byk Chemie社製) 0.4g
・Klucel M(Hercules社製) 4.8g
・ELVACITE 4026(Ineos Acrylics社製)
2.5g
・アニオン界面活性剤1〔上記構造〕 0.15g
・n-プロパノール 55.0g
・2-ブタノン 17.0g
・IRGACURE 250:(4-メチルフェニル)[4-(2-メチルプロピル)フェニル]ヨードニウム=ヘキサフルオロホスファート(75質量%プロピレンカーボナート溶液)
・SR-399:ジペンタエリスリトールペンタアクリレート
・Byk 336:変性ジメチルポリシロキサン共重合体(25質量%キシレン/メトキシプロピルアセテート溶液)
・Klucel M:ヒドロキシプロピルセルロース(2質量%水溶液)
・ELVACITE 4026:高分岐ポリメチルメタクリレート(10質量%2-ブタノン溶液)
1000mlの4つ口フラスコに撹拌機、温度計、滴下ロート、窒素導入管、還流冷却器を施し、窒素ガスを導入して脱酸素を行いつつ、ポリエチレングリコールメチルエーテルメタクリレート(PEGMA エチレングリコールの平均の繰返し単位は20)10g、蒸留水200g及びn-プロパノール200gを加えて内温が70℃となるまで加熱した。次に予め混合されたスチレン(St)10g、アクリロニトリル(AN)80g及び2,2’-アゾビスイソブチロニトリル0.8gの混合物を1時間かけて滴下した。滴下終了後5時間そのまま反応を続けた後、2,2’-アゾビスイソブチロニトリル0.4gを添加し、内温を80℃まで上昇させた。続いて、0.5gの2,2‘-アゾビスイソブチロニトリルを6時間かけて添加した。合計で20時間反応させた段階で高分子化合物化は98%以上進行しており、質量比でPEGMA/St/AN=10/10/80の高分子化合物微粒子水分散液(1)が得られた。この高分子化合物微粒子の粒径分布は、粒子径150nmに極大値を有していた。
平版印刷版原版を図2に示すような回転刃を用いて、上側裁断刃と下側裁断刃の隙間、噛み込み量及び刃先角度を調整して、所望のダレ量及びダレ幅を有する端部の形状となるように連続的にスリットした。
平版印刷版原版を赤外線半導体レーザー搭載の富士フイルム(株)製Luxel PLATESETTER T-6000IIIにて、外面ドラム回転数1000rpm、レーザー出力70%、解像度2400dpiの条件で露光した。露光画像にはベタ画像及び50%網点チャートを含むようにした。
下記表1に記載した化合物を純水に溶解して、処理液A~Iを調製した。括弧内の数字は化合物の濃度(質量%)を表す。
表1において、商品名で記載した化合物は以下の通りである。
・ニューコールB13 (非イオン性界面活性剤、ポリオキシエチレンアリールエーテル、日本乳化剤(株)製)
・ペレックスNBL (アニオン性界面活性剤、アルキルナフタレンスルホン酸ナトリウム、花王(株)製)
・ラピゾールA-80 (アニオン性界面活性剤、ジ(2-エチルヘキシル)スルホコハク酸ナトリウム、日油(株)製)
(塗布方法1)
塗布装置として、非接触ディスペンサー方式の武蔵エンジニアリング(株)社製AeroJetを使用した。クリアランス6mm、吐出圧0.05MPaの条件で、塗布量(固形分)が0.8g/m2になるように搬送速度を調整して、平版印刷版原版の端部から0.3cmの領域に上記処理液を塗布した後、エスペック(株)製恒温器PH-201を用いて120℃で1分間乾燥した。
(塗布方法2)
上記処理液を含ませた布を平版印刷版原版の端部に接触させ、端部に沿って布を滑らせながら平版印刷版原版の端部から少なくとも0.5cmの領域に、塗布方法1とほぼ同じ塗布量となるよう処理液を塗布した後、エスペック(株)製恒温器PH-201を用いて120℃で1分間乾燥した。
(塗布方法3)
上記処理液を含ませた布を平版印刷版原版の端部に接触させ、布を上から押さえつけて平版印刷版原版の端部から少なくとも0.5cmの領域に、塗布方法1とほぼ同じ塗布量となるよう処理液を塗布した後、エスペック(株)製恒温器PH-201を用いて120℃で1分間乾燥した。
(塗布方法4)
上記処理液を含ませた刷毛を平版印刷版原版の端部に接触させて平版印刷版原版の端部から少なくとも0.5cmの領域に、塗布方法1とほぼ同じ塗布量となるよう処理液を塗布した後、エスペック(株)製恒温器PH-201を用いて120℃で1分間乾燥した。
(エッジ汚れの評価)
<標準水目盛り条件での印刷>
上記のようにして画像露光後に端部を処理した平版印刷版原版を、オフセット輪転印刷機に装着し、新聞用印刷インキとして、インクテック(株)製のソイビーKKST-S(紅)及び湿し水として、東洋インキ(株)製の東洋ALKYを用いて、100,000枚/時のスピード、標準水目盛りで印刷し、1,000枚目の印刷物をサンプリングして、エッジ部の線状汚れの程度を下記の基準で評価した。
5:全く汚れていない
4:5と3の中間レベル
3:うっすらと汚れているが許容レベル
2:3と1の中間レベル
1:はっきりと汚れており非許容レベル
<標準水目盛りから水量15%減の条件での印刷>
湿し水の量を、標準水目盛りから15%減に変更する以外は、上記と同様に印刷を行い、同様に評価した。
結果を表2に示す。
上記標準水目盛り条件で印刷した1,000枚目の印刷物について、処理液塗布部と非塗布部の境界付近の領域(エッジ部近傍領域)における未露光部の汚れの程度を下記の基準で評価した。
3:非画像部は汚れていない。
2:非画像部はわずかに汚れている。
1:非画像部はかなり汚れている。
本出願は、2014年2月26日出願の日本特許出願(特願2014-035791)に基づくものであり、その内容はここに参照として取り込まれる。
1a 画像記録層面
1b 支持体面
1c 端面
2 ダレ
10 裁断刃
10a 上側裁断刃
10b 上側裁断刃
11 回転軸
20 裁断刃
20a 下側裁断刃
20b 下側裁断刃
21 回転軸
30 平版印刷版原版
X ダレ量
Y ダレ幅
B 画像記録層と支持体との境界
Claims (9)
- 支持体上に画像記録層を有する機上現像型平版印刷版原版を画像露光した後、印刷機に装着する前に、平版印刷版原版の版面の端部から1cm以内の領域に親水化剤を含有する処理液を塗布する機上現像型平版印刷版原版の処理方法であって、前記塗布を、塗布手段が版面に接触しないように行う処理方法。
- 前記塗布手段が、液体定量吐出装置である請求項1に記載の処理方法。
- 前記平版印刷版原版の端部が、ダレ量Xが35~150μm、ダレ幅Yが50~300μmのダレ形状を有する請求項1又は2に記載の処理方法。
- 前記親水化剤が、リン酸化合物、ホスホン酸化合物、アニオン性界面活性剤及び非イオン性界面活性剤から選択される少なくとも1つである請求項1~3のいずれか1項に記載の処理方法。
- 前記親水化剤が、リン酸化合物及びホスホン酸化合物から選択される少なくとも1つ並びにアニオン性界面活性剤及び非イオン性界面活性剤から選択される少なくとも1つである請求項4に記載の処理方法。
- 前記画像記録層が、赤外線吸収剤、重合開始剤、重合性化合物及びバインダーポリマーを含有する請求項1~5のいずれか1項に記載の処理方法。
- 前記画像記録層が、赤外線吸収剤、重合開始剤、重合性化合物及び微粒子形状の高分子化合物を含有する請求項1~5のいずれか1項に記載の処理方法。
- 前記画像記録層が、赤外線吸収剤及び熱可塑性微粒子ポリマーを含有する請求項1~5のいずれか1項に記載の処理方法。
- 請求項1~8のいずれか1項に記載の処理方法で処理された平版印刷版原版を、印刷機のシリンダーに装着し、インキ及び湿し水を供給して機上現像した後印刷する印刷方法。
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EP15755390.0A EP3112178B1 (en) | 2014-02-26 | 2015-02-16 | On-machine development type lithographic printing plate precursor processing method and printing method |
JP2016505153A JP6427555B2 (ja) | 2014-02-26 | 2015-02-16 | 機上現像型平版印刷版原版の処理方法及び印刷方法 |
BR112016019885-9A BR112016019885B1 (pt) | 2014-02-26 | 2015-02-16 | Método para processar um percursor de placa de impressão litográfica do tipo de desenvolvimento em prensa e método de impressão |
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Cited By (4)
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WO2018102136A1 (en) | 2016-12-02 | 2018-06-07 | Estman Kodak Company | Lithographic printing plate precursor and use |
WO2018159087A1 (ja) | 2017-02-28 | 2018-09-07 | 富士フイルム株式会社 | 平版印刷版の作製方法 |
WO2019044566A1 (ja) | 2017-08-31 | 2019-03-07 | 富士フイルム株式会社 | 平版印刷版原版、平版印刷版の作製方法及び平版印刷方法 |
WO2019188910A1 (ja) * | 2018-03-28 | 2019-10-03 | 富士フイルム株式会社 | 平版印刷版原版及び平版印刷版原版の製造方法 |
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CN107206827B (zh) * | 2015-01-29 | 2020-01-21 | 富士胶片株式会社 | 平版印刷版原版、其制造方法及利用其的印刷方法 |
US10414932B2 (en) * | 2015-10-20 | 2019-09-17 | Ricoh Company, Ltd. | Ink, ink container, and inkjet recording device |
CN110678335B (zh) * | 2017-05-31 | 2021-11-16 | 富士胶片株式会社 | 平版印刷版原版、平版印刷版的制作方法、聚合物粒子及组合物 |
JP6825113B2 (ja) | 2017-08-30 | 2021-02-03 | 富士フイルム株式会社 | 機上現像型平版印刷版原版、及び平版印刷版の作製方法 |
WO2019151447A1 (ja) * | 2018-01-31 | 2019-08-08 | 富士フイルム株式会社 | 機上現像型平版印刷版原版、平版印刷版の作製方法、機上現像型平版印刷版ダミー版、及び印刷方法 |
CN110239202B (zh) * | 2019-06-26 | 2023-06-23 | 云南卓印科技有限公司 | 一种平版印刷橡胶水辊及其制备方法 |
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WO2018102136A1 (en) | 2016-12-02 | 2018-06-07 | Estman Kodak Company | Lithographic printing plate precursor and use |
WO2018159087A1 (ja) | 2017-02-28 | 2018-09-07 | 富士フイルム株式会社 | 平版印刷版の作製方法 |
EP3879346A1 (en) | 2017-02-28 | 2021-09-15 | FUJIFILM Corporation | Method for producing lithographic printing plate |
WO2019044566A1 (ja) | 2017-08-31 | 2019-03-07 | 富士フイルム株式会社 | 平版印刷版原版、平版印刷版の作製方法及び平版印刷方法 |
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EP3112178B1 (en) | 2018-05-16 |
US20160361914A1 (en) | 2016-12-15 |
JPWO2015129504A1 (ja) | 2017-03-30 |
EP3112178A1 (en) | 2017-01-04 |
CN106170396A (zh) | 2016-11-30 |
BR112016019885A2 (pt) | 2021-06-22 |
JP6427555B2 (ja) | 2018-11-21 |
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BR112016019885B1 (pt) | 2022-05-03 |
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