WO2016047309A1 - 平版印刷版原版、その製造方法、及びそれを用いる印刷方法 - Google Patents
平版印刷版原版、その製造方法、及びそれを用いる印刷方法 Download PDFInfo
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- WO2016047309A1 WO2016047309A1 PCT/JP2015/072973 JP2015072973W WO2016047309A1 WO 2016047309 A1 WO2016047309 A1 WO 2016047309A1 JP 2015072973 W JP2015072973 W JP 2015072973W WO 2016047309 A1 WO2016047309 A1 WO 2016047309A1
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- WIPO (PCT)
- Prior art keywords
- printing plate
- plate precursor
- lithographic printing
- image recording
- recording layer
- Prior art date
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Classifications
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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
- B41C1/00—Forme preparation
- B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M1/00—Inking and printing with a printer's forme
- B41M1/06—Lithographic printing
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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
- B41N1/00—Printing plates or foils; Materials therefor
- B41N1/12—Printing plates or foils; Materials therefor non-metallic other than stone, e.g. printing plates or foils comprising inorganic materials in an organic matrix
- B41N1/14—Lithographic printing foils
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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
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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
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
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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
- B41C1/1016—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials characterised by structural details, e.g. protective layers, backcoat layers or several imaging layers
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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
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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
- B41C2210/20—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by inorganic additives, e.g. pigments, salts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41P—INDEXING SCHEME RELATING TO PRINTING, LINING MACHINES, TYPEWRITERS, AND TO STAMPS
- B41P2200/00—Printing processes
- B41P2200/20—Lithography
Definitions
- the present invention relates to a planographic printing plate precursor, a method for producing the same, and a printing method using the same.
- 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.
- thermoplastic polymer particles are contained in an image forming layer (see Patent Document 1). It is also known to provide a layer containing organic resin fine particles as a main component between a support and a photosensitive layer (see Patent Document 2).
- 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.
- An object of the present invention is to provide a lithographic printing plate precursor in which transfer of an image recording layer is prevented even when the lithographic printing plate precursor is stored in an overlapping manner without causing edge contamination, a method for producing the same, and a printing method using the same. Is to provide.
- the area per unit area of the fine particles contained in the area of the image recording layer side plate surface from the edge of the lithographic printing plate precursor having the image recording layer on the support to the inner side of 5 mm is an area other than the above area.
- the compound having a support adsorptive group is a phosphoric acid compound or a phosphonic acid compound.
- the image recording layer comprises an infrared absorber, a polymerization initiator, a polymerizable compound, and a binder polymer.
- the image recording layer contains an infrared absorber and a thermoplastic fine particle polymer.
- a method for producing a lithographic printing plate precursor on the support in the order of step a and step f. (19) The method for producing a lithographic printing plate precursor as described in (18), wherein (d) an undercoat layer forming step for forming an undercoat layer is performed on the support before step a.
- the lithographic printing plate precursor in which transfer of the image recording layer is prevented even when the lithographic printing plate precursor is stored in an overlapping manner without causing edge contamination, a method for producing the same, and a printing method using the same can be provided.
- the present invention is described in detail below.
- the lithographic printing plate precursor according to the present invention is a content per unit area of fine particles contained in a region of the image recording layer side plate surface from the end of the lithographic printing plate precursor having an image recording layer on the support to the inner side of 5 mm. Is more than the content per unit area of the fine particles in a region other than the region by 10 mg / m 2 or more.
- the constituent layers for example, an undercoat layer (also referred to as an intermediate layer), an image recording layer (also referred to as an image forming layer), and a protective layer (also referred to as an overcoat layer) may contain fine particles.
- an undercoat layer also referred to as an intermediate layer
- an image recording layer also referred to as an image forming layer
- a protective layer also referred to as an overcoat layer
- the fine particles are present almost uniformly in the plane of the planographic printing plate precursor. That is, the content of the fine particles is not substantially different between the central portion and the end portion of the lithographic printing plate precursor.
- the content of the fine particles in the edge region is reduced by means such as applying the coating liquid containing the fine particles only to the edge region of the lithographic printing plate precursor.
- the feature is that it is intentionally increased as compared with the region other than the end region.
- the content of fine particles per unit area in the region of the image recording layer side plate surface up to 5 mm inward from the end of the lithographic printing plate precursor is the content of fine particles per unit area in a region other than the region described above. more 10 mg / m 2 or more often it is a feature.
- the difference between the content of fine particles per unit area in the region of the image recording layer side plate surface up to 5 mm inward from the edge of the lithographic printing plate precursor and the content of fine particles per unit area in regions other than the above regions is as described above.
- a lithographic printing plate precursor having excellent edge stain resistance and preventing transfer of the image recording layer can be obtained.
- the difference in the content of the fine particles is preferably 10 to 5000 mg / m 2 , more preferably 30 to 1000 mg / m 2 , and particularly preferably 50 to 500 mg / m 2 .
- the end portion of the lithographic printing plate precursor means an edge portion formed by a step of cutting into a sheet or the like in the production process of the lithographic printing plate precursor.
- the sheet-like planographic printing plate precursor has four ends, top, bottom, left and right.
- the number of edges having a high fine particle content according to the present invention is 1 to 4 in relation to the size of the printing paper from the viewpoint of preventing edge smearing.
- two opposing sides of a planographic printing plate precursor that are in the printing paper surface usually correspond to the end portions.
- the area of the image recording layer side plate surface from the end to the inner side of 5 mm includes not only the image recording layer but also all layers provided on the image recording layer side of the support. Accordingly, the content per unit area of the fine particles in the region of the image recording layer side plate surface from the end to the inner side of 5 mm is from the end on the image recording layer side of the lithographic printing plate precursor to the inner side of the lithographic printing plate precursor. It means the total content of fine particles present per unit area in a region up to 5 mm. Similarly, the content per unit area of fine particles in a region other than the above region means the total content of fine particles present per unit area in the region.
- an area of 5 mm from the end to the inside is also referred to as an end area.
- a region other than the end region is also referred to as other region.
- the content of fine particles per unit area in the end region and other regions can be determined as follows. Prepare samples corresponding to the edge area and other areas of the lithographic printing plate precursor, and remove the entire coating film on the support using a solvent such as water, an organic solvent, or a mixture thereof for each sample. The membrane solution is centrifuged to separate the fine particles, the mass of the fine particles is measured, and the mass is converted to a unit area (m 2 ) to thereby contain the fine particles per unit area in the end region and other regions. The amount can be determined.
- a normal fine particle separation method is used.
- the method of filtering with a filter etc. the method of precipitating microparticles
- the filter filtration device for example, a device such as reduced pressure or pressure filtration can be used.
- preferable filters include filter paper, nanofilters, and ultrafilters.
- the centrifuge need only be a device capable of precipitating fine particles.
- a skimming function a function of sucking the supernatant layer during rotation and discharging it out of the system
- Examples include a continuous centrifuge that continuously discharges solid matter.
- Centrifugation conditions are preferably 50 to 50000, more preferably 100 to 40000, and particularly preferably 150 to 30000 in terms of centrifugal force (a value representing how many times the gravity acceleration is applied).
- the temperature at the time of centrifugation depends on the type of solvent used, but is preferably ⁇ 10 to 80 ° C., more preferably ⁇ 5 to 70 ° C., and particularly preferably 0 to 60 ° C.
- the solvent removal step is generally removal by decantation, but a method of concentrating the solvent by vacuum freeze-drying, a method of concentrating by drying the solvent by heating or decompression, and a combination thereof. A method or the like can also be used.
- the fine particles contained in the end region of the lithographic printing plate precursor according to the invention may be either organic fine particles or inorganic fine particles as long as they are present in the fine particle form in the lithographic printing plate precursor.
- Various fine particles known to be contained in the constituent layers of the planographic printing plate precursor for example, the undercoat layer, the image recording layer, and the protective layer may be used. Due to the presence of the fine particles, in the on-press development type lithographic printing plate precursor, the permeability of the fountain solution is improved, and the on-press development is promoted, whereby the edge stain is considered to be eliminated.
- organic resin fine particles such as microgel (crosslinked polymer fine particles) and thermoplastic fine particles are preferably used as the organic fine particles.
- a microgel is a reactive or non-reactive resin particle dispersed in an aqueous medium.
- the microgel may be in the form of a reactive microgel by having a polymerizable group in the particle surface or on the particle surface, preferably on the particle surface.
- the resin constituting the particles is preferably polyurea, polyurethane, polyester, polycarbonate, polyamide, and a mixture thereof, more preferably polyurea and polyurethane, and particularly preferably polyurethane.
- the microgel can be prepared by a known method. For example, a monohydric alcohol having an ethylenically unsaturated group is reacted with an adduct of a polyhydric alcohol and a diisocyanate, and dissolved in ethyl acetate together with a small amount of a surfactant to prepare an oily component.
- an aqueous component an aqueous solution of polyvinyl alcohol is prepared.
- An oily component and an aqueous component are mixed, and the mixture is emulsified and dispersed by high-speed stirring with a mechanical stirrer, and the solid content concentration is adjusted to obtain a microgel.
- thermoplastic fine particles examples 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, European Patent 931647, and the like can be preferably exemplified. .
- thermoplastic fine particles examples include ethylene, styrene, vinyl chloride, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, vinylidene chloride, acrylonitrile, vinyl carbazole, and acrylate having a polyalkylene structure. Or homopolymers or copolymers of monomers such as methacrylates or mixtures thereof. Among these, a copolymer containing polystyrene, styrene and acrylonitrile, and polymethyl methacrylate are preferable.
- inorganic fine particles include metals and metal compounds such as oxides, composite oxides, hydroxides, carbonates, sulfates, silicates, phosphates, organic acid salts, Examples thereof include nitrides, carbides, sulfides, and composites of at least two of these.
- silica, alumina, magnesium oxide, titanium oxide, magnesium carbonate, calcium alginate, or a mixture thereof can be used.
- the shape of the fine particles according to the present invention may be any shape such as a spherical shape, a needle shape, a flat plate shape, a feather shape, a chain shape (beaded shape), an amorphous shape, etc., but a spherical shape is preferable.
- the average particle size of the fine particles is preferably 5 ⁇ m or less, more preferably 0.005 to 3 ⁇ m, and particularly preferably 0.01 to 2 ⁇ m.
- a known method can be used to measure the particle diameter. Specific examples include laser diffraction / scattering methods, dynamic light scattering methods, static light scattering methods, dynamic imaging methods, static imaging methods, image analysis methods, and electron microscopy.
- a fine particle-containing liquid is diluted with distilled water or the like so that the particle concentration is 0.1 to 1% by weight, and a commercially available average particle size measuring device (for example, LA-910 (manufactured by Horiba, Ltd.)) Can be measured easily.
- a commercially available average particle size measuring device for example, LA-910 (manufactured by Horiba, Ltd.)
- the dynamic light scattering method using the laser Doppler effect is preferable because it can measure the particle size up to a small size.
- the lithographic printing plate precursor for example, a method of observing a section of the lithographic printing plate precursor with an electron microscope or an image analysis method is preferable because the particle size can be easily measured.
- the particle diameter of the fine particles is a numerical value measured using a laser diffraction / scattering method (measuring device: LA-910, manufactured by Horiba, Ltd.).
- the fine particles according to the present invention can be contained at any position from the support constituting the lithographic printing plate precursor to the uppermost layer.
- the fine particles are between the support and the undercoat layer, in the undercoat layer, and between the undercoat layer and the image recording layer. They may be present in any position in the image recording layer, between the image recording layer and the protective layer, in the protective layer, or on the protective layer.
- the fine particles may be present at a plurality of positions.
- the fine particle-containing position according to the present invention is preferably present between the support and the image recording layer.
- a coating solution containing the fine particles can be applied to a specific position of the lithographic printing plate precursor. A specific method will be described later as a method for producing a lithographic printing plate precursor.
- the region of the image recording layer side plate surface from the end portion to 5 mm inward from the end portion further contains a hydrophilic compound.
- the hydrophilic compound has an effect of preventing stains caused by the printing ink accumulating by hydrophilizing a crack that may occur during the formation of a sagging shape, which will be described later.
- a water-soluble compound is preferable.
- any compound can be used as long as it is a compound that can dissolve 0.5 g or more in 100 g of water at 20 ° C. A compound that dissolves 2 g or more in 100 g of water at 20 ° C. is more preferable.
- the hydrophilic compound preferably has a support adsorptive group.
- the support adsorptive group is an adsorptive group that can be adsorbed on the support surface of the lithographic printing plate precursor, and preferred examples thereof include phenolic hydroxy groups, carboxy groups, —PO 3 H 2 groups, —OPO 3 H 2 groups. Group, -CONHSO 2 -group, -SO 2 NHSO 2 -group, -COCH 2 COCH 3 group. Of these, —PO 3 H 2 group and —OPO 3 H 2 group are particularly preferred.
- a phosphoric acid compound and a phosphonic acid compound which are compounds having a —PO 3 H 2 group and a —OPO 3 H 2 group, will be described in detail.
- the phosphoric acid compound includes phosphoric acid, a salt thereof, an ester thereof, and the like.
- Examples include potassium and sodium hexametaphosphate. Of these, sodium dihydrogen phosphate, sodium monohydrogen phosphate, and sodium hexametaphosphate are preferably used.
- the phosphoric acid compound a polymer compound is preferable, and a polymer compound having a phosphoric acid monoester group is more preferable.
- a coating solution containing fine particles having excellent coating properties can be obtained.
- the polymer compound having a phosphate ester group include a polymer comprising one or more monomers having a phosphate ester group in the molecule, or one or more monomers having a phosphate ester group and phosphorus. Examples thereof include a copolymer with one or more monomers not containing an acid ester group, and a polymer in which a phosphate ester group is introduced into a polymer having no phosphate ester group by a polymer reaction.
- Monomers having a phosphate ester group include mono (2-methacryloyloxyethyl) acid phosphate, mono (2-methacryloyloxypolyoxyethylene glycol) acid phosphate, mono (2-acryloyloxyethyl) acid phosphate, 3- Chloro-2-acid phosphooxypropyl methacrylate, acid phosphooxypolyoxyethylene glycol monomethacrylate, acid phosphooxypolyoxypropylene glycol methacrylate, (meth) acryloyloxyethyl acid phosphate, (meth) acryloyloxypropyl acid phosphate, (meth) Acryloyloxy-2-hydroxypropyl acid phosphate, (meth) acryloyloxy-3-hydroxypropyl Cyd phosphate, (meth) acryloyloxy-3-chloro-2-hydroxypropyl acid phosphate, and the like allyl alcohol acid phosphate.
- mono (2-acryloyloxyethyl) acid phosphate is preferably used from the viewpoint of assisting in preventing edge stains.
- Typical commercial products include Light Ester P-1M (manufactured by Kyoei Chemical Co., Ltd.) and Phosmer PE (manufactured by Unichemical Co., Ltd.).
- the monomer having no phosphate group in the copolymer is preferably a monomer having a hydrophilic group.
- the hydrophilic group include a hydroxy group, an alkylene oxide structure, an amino group, an ammonium group, and an amide group.
- a hydroxy group, an alkylene oxide structure, and an amide group are preferable, and an alkylene oxide unit having 2 or 3 carbon atoms. Is more preferable, and a polyethylene oxide structure having 2 to 10 ethylene oxide units is more preferable.
- Examples thereof include 2-hydroxyethyl acrylate, ethoxydiethylene glycol acrylate, methoxytriethylene glycol acrylate, poly (oxyethylene) methacrylate, N-isopropylacrylamide, and acrylamide.
- the ratio of the repeating unit having a phosphate ester group is preferably 1 to 100 mol%, more preferably 5 to 100 mol%, and still more preferably 10 to 100 mol%.
- the weight average molecular weight of the polymer compound having a phosphate ester group is preferably 5,000 to 1,000,000, more preferably 7,000 to 700,000, and particularly preferably 10,000 to 500,000.
- the phosphonic acid compound includes phosphonic acid, a salt thereof, an ester thereof, and the like.
- a polymer compound is preferable.
- a coating solution containing fine particles having excellent coating properties can be obtained.
- Preferred polymer compounds as the phosphonic acid compound include polyvinylphosphonic acid, a polymer comprising one or more monomers having a phosphonic acid group or a phosphonic acid monoester group in the molecule, a phosphonic acid group or a phosphonic acid monoester group And one or more monomers having a phosphonic acid group or one or more monomers not containing a phosphonic acid monoester group.
- the monomer having a phosphonic acid group include vinylphosphonic acid, ethylphosphonic acid monovinyl ester, acryloylaminomethylphosphonic acid, and 3-methacryloyloxypropylphosphonic acid.
- the polymer compound either a homopolymer or a copolymer of a monomer having a phosphonic acid ester group is used.
- the copolymer include a copolymer of a monomer having a phosphonic acid ester group and a monomer having a hydrophilic group, a monomer having a phosphonic acid ester group, a phosphonic acid ester group, and a hydrophilic property. Copolymers with monomers that do not contain either group can be used.
- the hydrophilic group of the monomer having a hydrophilic group in the copolymer include a hydroxy group, an alkylene oxide structure, an amino group, an ammonium group, and an amide group.
- a hydroxy group, an alkylene oxide structure, Amide groups are preferred, alkylene oxide structures having 1 to 20 alkylene oxide units having 2 or 3 carbon atoms are more preferred, and polyethylene oxide structures having 2 to 10 ethylene oxide units are more preferred. Examples thereof include 2-hydroxyethyl acrylate, ethoxydiethylene glycol acrylate, methoxytriethylene glycol acrylate, poly (oxyethylene) methacrylate, N-isopropylacrylamide, acrylamide and the like.
- the ratio of the repeating unit having a phosphonic acid ester group is 1 to 100 mol%, more preferably 3 to 100 mol%, still more preferably 5 to 100 mol%.
- the weight average molecular weight of the polymer compound having a phosphonic acid ester group is preferably 5,000 to 1,000,000, more preferably 7,000 to 700,000, and particularly preferably 10,000 to 500,000.
- the hydrophilic compound in the region of the image recording layer side plate surface up to 5 mm from the end to the inside, it is preferable from the viewpoint of workability that the fine particles are applied together when applied to the lithographic printing plate precursor. Specifically, it can be easily carried out by adding a hydrophilic compound to the coating solution containing fine particles and coating it.
- the planographic printing plate precursor according to the invention has an image recording layer on a support.
- the planographic printing plate precursor may have an undercoat layer between the support and the image recording layer and a protective layer on the image recording layer, if necessary.
- 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 acidic to alkaline dampening water and printing ink on a printing machine.
- 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, R a 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, and 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.
- Me represents a methyl group.
- 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. It is 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-shaped polymer compound is a star-shaped polymer compound having a polyoxyalkylene chain (for example, the group represented by the general formula (1) or (2)) on the side
- 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 include those described in paragraph numbers [0153] to [0157] of JP-A-2014-104631.
- 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.
- ⁇ Formation of image recording layer A> For the image recording layer A, for example, as described in paragraphs [0142] to [0143] of JP-A-2008-195018, the necessary components described above are dispersed or dissolved in a known solvent to prepare a coating solution. Then, this coating solution is formed on the support directly or through an undercoat layer by a known method such as bar coater coating and then dried.
- 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.), a carboxy group that performs a condensation reaction, and 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
- 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 C is formed by preparing or applying a coating solution by dissolving or dispersing the necessary components described above in an appropriate solvent, and coating the coating solution directly or via an undercoat layer.
- a coating solution by dissolving or dispersing the necessary components described above in an appropriate solvent, and coating the coating solution directly or via an undercoat layer.
- the 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 lower 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.
- an undercoat layer can be provided between the image recording layer and the support, if necessary.
- 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. Of these, 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 can be provided on the image recording layer as necessary.
- 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 a function is described in, for example, US Pat. No. 3,458,311 and JP-B-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 according to the invention is characterized in that the end region has a structure containing fine particles with a higher content than other regions.
- the production method of the lithographic printing plate precursor is not particularly limited. Below, the manufacturing method of the lithographic printing plate precursor which concerns on this invention is illustrated.
- the fine particles can be introduced into the end region of the lithographic printing plate precursor by applying the coating liquid containing the fine particles to the end region of the lithographic printing plate precursor in the production process of the lithographic printing plate precursor.
- the timing of applying the coating solution containing fine particles to the end region of the lithographic printing plate precursor may be any of the manufacturing processes of the lithographic printing plate precursor, before and after the step of forming each constituent layer, that is, the lowermost layer (for example, It is preferable from before application of the undercoat layer to after drying of the uppermost layer (for example, protective layer).
- the cutting of the lithographic printing plate precursor may be performed before or after the coating liquid containing fine particles is applied to the end region of the lithographic printing plate precursor.
- the edge region of the lithographic printing plate precursor is formed.
- the coating solution containing fine particles is applied to the edge of the lithographic printing plate precursor.
- the position corresponding to the edge area means a position where an area on the image recording layer side plate surface of 5 mm inward from the edge can be formed in the lithographic printing plate precursor after cutting.
- the position corresponding to the end region may be a position near the end of the lithographic printing plate precursor or a position near the center of the lithographic printing plate precursor in the production process of the lithographic printing plate precursor.
- two lithographic printing plate precursors having end regions are obtained by cutting so that the end regions are formed according to the fine particle coating region.
- the edge region of the lithographic printing plate precursor is formed.
- the following method is preferably exemplified as the cutting method.
- a lithographic printing plate precursor having an image recording layer on a support
- Examples of the method for producing a lithographic printing plate precursor include a step a and a step b on the support, or a step b and a step, followed by a step c.
- a protective layer forming step for forming a protective layer may be performed on the image recording layer.
- a lithographic printing plate precursor having an undercoat layer and an image recording layer in this order on a support, (A) an image recording layer forming step for forming the image recording layer; (B) a coating step of coating the coating liquid containing the fine particles so as to overlap a partial region of the image recording layer formed in step a; (C) a cutting step of cutting so that the area where the coating solution is applied is within the range of the image recording layer side plate surface up to 5 mm from the edge of the lithographic printing plate precursor after cutting; and (d) the undercoat Undercoat layer forming step of forming a layer, On the support, it is performed in the order of b process, d process and a process, or in the order of d process, b process and a process, or in the order of d process, a process and b process. Examples include a method for producing a lithographic printing plate precursor for performing step c.
- a lithographic printing plate precursor having an undercoat layer, an image recording layer and a protective layer in this order on the support, (A) an image recording layer forming step for forming the image recording layer; (B) a coating step of coating the coating liquid containing the fine particles so as to overlap a partial region of the image recording layer formed in step a; (C) a cutting step of cutting so that the area where the coating solution is applied is within the range of the image recording layer side plate surface up to 5 mm from the end of the lithographic printing plate precursor after cutting; (D) an undercoat layer forming step for forming the undercoat layer, and (E) a protective layer forming step for forming the protective layer, On the support, it is carried out in the order of b process, d process, a process and e process, or in the order of d process, b process, a process and e process, or d process, a process, b process and e. Examples include a method for producing a lithographic printing plate precursor, which is performed
- the following method is preferably exemplified.
- a lithographic printing plate precursor having an image recording layer on a support
- a method for producing a lithographic printing plate precursor which is carried out in the order of step a and step f on the support, is mentioned. Further, after the step a and before the step f, (e) a protective layer forming step for forming a protective layer may be performed on the image recording layer.
- a lithographic printing plate precursor having an undercoat layer, an image recording layer and a protective layer in this order on the support, (A) an image recording layer forming step for forming the image recording layer; (F) a coating step of coating the coating liquid containing the fine particles on an area of 5 mm inward from the end of the lithographic printing plate precursor; (D) an undercoat layer forming step for forming the undercoat layer, and (E) a protective layer forming step for forming the protective layer,
- a method for producing a lithographic printing plate precursor which is carried out in the order of step d, step a, step e, step f on the support, can be mentioned.
- the step of forming the constituent layer includes at least a step of applying the constituent layer.
- the step of drying the coating layer after applying the constituent layer is not necessarily required for the step of forming the constituent layer.
- a coating solution containing fine particles can be applied without drying. In this case, it is considered that the fine particles are present not only on the undercoat layer but also in the undercoat layer.
- the fine particle-containing coating solution is a coating solution containing the fine particles described above.
- the fine particle-containing coating liquid has a form of an aqueous dispersion in which fine particles are dispersed in a medium mainly composed of water.
- the fine particle-containing coating solution preferably contains the hydrophilic compound.
- the content of the hydrophilic compound in the fine particle-containing coating solution is preferably 0.03 to 20.0% by mass, and more preferably 0.05 to 10% by mass based on the total mass of the fine particle-containing coating solution.
- the fine particle-containing coating liquid preferably contains a water-soluble resin.
- the water-soluble resin has an effect of preventing stains caused by printing ink collecting by hydrophilizing cracks that may occur during the formation of a sag shape, which will be described later.
- 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 fine particle-containing coating solution. Within this range, the effect of the water-soluble resin is satisfactorily achieved.
- the fine particle-containing coating solution may further contain a surfactant, an organic solvent, a plasticizer, and other additives.
- surfactant examples include an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant. Anionic surfactants and nonionic surfactants are preferred.
- the surfactant has an effect of improving the dispersion stability of the fine particles and preventing the fine particles from agglomerating and settling.
- Anionic surfactants include fatty acid salts, abietic acid salts, hydroxyalkane sulfonates, alkane sulfonates, dialkyl sulfosuccinates, benzene sulfonates, linear alkyl benzene sulfonates, branched alkyl benzene sulfonates, Naphthalene sulfonates, alkyl naphthalene sulfonates, alkylphenoxy polyoxyethylene propyl sulfonates, polyoxyethylene aryl ether sulfates, polyoxyethylene alkyl sulfophenyl ethers, N-methyl-N-oleyl taurine sodium, N-alkylsulfosuccinic acid monoamide disodium salts, petroleum sulfonates, sulfated castor oil, sulfated tallow oil, sulfate esters of fatty acid alkyl esters,
- 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 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 monofatty 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 moieties Esters, fatty acid diethanolamides, N, N-bis-2-hydroxyalkylamines, polyoxyethylene alkylamines, trie Noruamin fatty acid esters, trialkylamine oxides, polyoxyethylene - polyoxypropylene block copolymers can be mentioned.
- 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 surfactant represented by the general formula (II-A) are shown below.
- 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 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 surfactant in the fine particle-containing coating solution is preferably 0.01 to 20% by mass, and more preferably 0.1 to 15% by mass based on the total mass of the coating solution.
- Organic solvent can be contained for the purpose of adjusting the solubility of the water-soluble resin and promoting 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 fine particle-containing coating solution. Within this range, the effect of the organic solvent is satisfactorily achieved.
- 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 bit, and a phosphate esters such as
- 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 fine particle-containing coating solution.
- the fine particle-containing coating solution 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 fine particle-containing coating liquid may be prepared by mixing and dispersing fine particles and components such as additives to be used as necessary in a solvent such as water (distilled water, ion-exchanged water, demineralized water, etc.).
- a solvent such as water (distilled water, ion-exchanged water, demineralized water, etc.).
- a fine particle dispersion in which fine particles are dispersed in a solvent may be prepared in advance, and then other additives and the like may be added and mixed therewith.
- the content of the fine particles in the fine particle-containing coating solution is preferably 0.05 to 50% by mass, more preferably 0.1 to 30% by mass, and particularly preferably 0.2 to 20% by mass.
- the viscosity of the coating solution containing fine particles is preferably 0.5 to 1000 mPa ⁇ s, more preferably 1 to 100 mPa ⁇ s at 25 ° C. When the viscosity is within the above range, bead fracture is less likely to occur, and this is preferable in that the application at the start of coating is good.
- the surface tension of the fine particle-containing coating solution is preferably 25 to 70 mN / m, more preferably 40 to 65 mN / m at 25 ° C. When the surface tension is within the above range, it is preferable in that the coating width can be easily controlled and bead fracture is less likely to occur.
- the fine particle-containing coating solution is applied to a position corresponding to the end region in the manufacturing process of the lithographic printing plate precursor.
- variety the area
- the fine particle-containing coating solution is applied after cutting
- a coating method using a cloth or a Morton roll impregnated with the fine particle-containing coating solution can be used in addition to the above coating method.
- the coating amount of the fine particle-containing coating liquid, as a solid after drying is preferably 0.01 ⁇ 6.0g / m 2, more preferably 0.03 ⁇ 3.0g / m 2, 0.05 ⁇ 2.0g / M 2 is particularly preferred.
- Drying is performed after application of the fine particle-containing coating solution. Drying may be performed after the application of the fine particle-containing coating solution, or may be performed after the coating solution for forming the constituent layer of the lithographic printing plate precursor is applied. Drying can be performed by using an oven or blowing dry air.
- the drying temperature is preferably 60 to 220 ° C, more preferably 80 to 180 ° C.
- the lithographic printing plate precursor is cut in the production process of the lithographic printing plate precursor as described above. Cutting can be performed using a known cutting method. Preferably, the methods described in JP-A-8-58257, JP-A-9-211843, JP-A-10-100556, and JP-A-11-52579 can be used.
- the end of the planographic printing plate precursor preferably has a sagging shape.
- the lithographic printing plate precursor having a sag shape at the end portion is excellent in edge stain prevention effect in combination with the fine particle-containing end portion region 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 sag at the edge of the lithographic printing plate precursor is preferably 35 ⁇ m or more, and more preferably 40 ⁇ m or more.
- the upper limit of the sagging amount is preferably 150 ⁇ m from the viewpoint of preventing deterioration of on-press developability due to deterioration of the end surface condition.
- the on-machine developability deteriorates, ink adheres to the remaining photosensitive layer and causes edge smearing.
- the sagging amount is less than 35 ⁇ m, the ink adhering to the end portion is easily transferred to the blanket and may cause edge smearing.
- 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 70 to 300 ⁇ m, and preferably in the range of 80 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 similarly to 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.
- the plate making of the lithographic printing plate precursor according to the present invention is described below.
- a preferred embodiment of the plate making of the lithographic printing plate precursor according to the invention includes image exposure and on-press development.
- the image exposure of the lithographic printing plate precursor can be performed according to the normal image exposure operation of the 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 can be performed by conventional methods. That is, when dampening water and printing ink are supplied to the lithographic printing plate precursor subjected to image exposure on a printing machine, the image recording layer cured by exposure has an oleophilic surface in the exposed portion of the image recording layer. A printing ink receiving portion is formed. On the other hand, in the unexposed area, 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.
- a plate making system used for processing with an ordinary developer can also be used. That is, an exposure unit for image exposure of the lithographic printing plate precursor with an exposure machine, a development processing unit for removing an unexposed part of the lithographic printing plate precursor image-exposed by the exposure unit with an automatic developing machine, and the lithographic printing plate precursor to the printing machine
- a plate making system having processing portions in this order for processing by a punch bender for mounting can be used.
- plate making may be performed by a system excluding the development processing unit, or plate making can be performed with the development processing unit remaining.
- the development processing, water washing and finisher sections are operated without charging the developer, water, and gum solution used in the development processing section.
- the part can be used as a transport device from the exposure part to the processing part.
- it is a transport device that can transport the insertion roller section and the discharge roller section of the development processing section without contacting the photosensitive layer side surface of the planographic printing plate transported like a belt conveyor with any part of the transport path.
- the developing unit, the water washing unit, and the finisher unit can be skipped, so that it can be used as a conveying device from the exposure unit to the processing unit.
- the lithographic printing plate precursor according to the present invention has excellent properties that no edge stains occur and the transfer of the image recording layer is prevented even when the lithographic printing plate precursors are stored in an overlapping manner. This characteristic is remarkable in the on-press development type lithographic printing plate precursor.
- the lithographic printing plate precursor according to the present invention exhibits its excellent characteristics.
- the width of the lithographic printing plate precursor corresponds to the lateral length of the lithographic printing plate precursor when attached to the plate cylinder of the printing press. Therefore, the lithographic printing plate precursor according to the present invention exhibits particularly excellent characteristics as an on-press development type lithographic printing plate precursor used for newspaper printing.
- the molecular weight is a mass average molar mass (Mw), and the ratio of the repeating units is a mole percentage except for those specifically defined.
- A Mechanical roughening treatment (brush grain method) Using an apparatus as shown in FIG. 3, mechanical roughening is performed by a rotating bundle-planting brush while supplying a suspension of pumice (specific gravity: 1.1 g / cm 3 ) as a polishing slurry to the surface of an aluminum plate.
- a suspension of pumice specifically gravity: 1.1 g / cm 3
- 41 is an aluminum plate
- 42 and 44 are roller-like brushes (bundling brushes in this embodiment)
- 43 is an abrasive slurry
- 45, 46, 47 and 48 are support rollers.
- the mechanical surface roughening treatment was performed with the median diameter of the abrasive pumice being 30 ⁇ m, the number of bundled brushes being 4, and the number of rotations of the bundled brush being 250 rpm.
- the material of the bunch planting brush was 6 ⁇ 10 nylon, with a bristle diameter of 0.3 mm and a bristle length of 50 mm.
- the bundle-planting brush is a tube made by making a hole in a stainless steel tube of ⁇ 300 mm so as to be dense. The distance between the two support rollers ( ⁇ 200 mm) at the bottom of the bundle-planting brush was 300 mm.
- the bundle brush was pressed until the load of the drive motor for rotating the brush became 10 kW plus with respect to the load before the bundle brush was pressed against the aluminum plate.
- the rotation direction of the bundle planting brush was the same as the movement direction of the aluminum plate.
- Electrochemical roughening treatment An electrochemical roughening treatment was carried out continuously using an alternating voltage of 60 Hz.
- an electrolytic solution an electrolytic solution in which aluminum nitrate was added to an aqueous solution having a temperature of 35 ° C. and nitric acid was 10.4 g / L to adjust the aluminum ion concentration to 4.5 g / L was used.
- the AC power supply waveform is subjected to electrochemical surface roughening using a carbon electrode as a counter electrode using a trapezoidal rectangular wave alternating current with a time tp of 0.8 msec until the current value reaches a peak from zero, a duty ratio of 1: 1. went. Ferrite was used for the auxiliary anode.
- FIG. 4 an aluminum plate W is wound around a radial drum roller 52 disposed so as to be immersed in the main electrolytic cell 50, and subjected to electrolytic treatment by main electrodes 53a and 53b connected to an AC power source 51 in the course of conveyance.
- the electrolytic solution 55 was supplied from the electrolytic solution supply port 54 through the slit 56 to the electrolytic solution passage 57 between the radial drum roller 52 and the main electrodes 53a and 53b.
- the aluminum plate W treated in the main electrolytic cell 50 was then electrolytically treated in the auxiliary anode cell 60.
- An auxiliary anode 58 is disposed opposite to the aluminum plate W in the auxiliary anode tank 60, and the electrolytic solution 55 is supplied so as to flow in the space between the auxiliary anode 58 and the aluminum plate W.
- 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 was 185 C / dm 2 as the total amount of electricity when the aluminum plate was an anode. Then, water washing by spraying was performed.
- desmutting treatment was performed in an aqueous sulfuric acid solution.
- an aqueous sulfuric acid solution having a sulfuric acid concentration of 170 g / L and an aluminum ion concentration of 5 g / L was used.
- the liquid temperature was 60 ° C.
- the desmutting treatment was performed by spraying a desmutting solution for 3 seconds.
- Electrochemical surface roughening treatment An electrochemical surface roughening treatment was performed continuously using an alternating voltage of 60 Hz.
- an electrolytic solution an electrolytic solution in which aluminum chloride was adjusted to 4.5 g / L by adding aluminum chloride to an aqueous solution having a liquid temperature of 35 ° C. and hydrochloric acid of 6.2 g / L was used.
- the AC power supply waveform is subjected to electrochemical surface roughening using a carbon electrode as a counter electrode using a trapezoidal rectangular wave alternating current with a time tp of 0.8 msec until the current value reaches a peak from zero, a duty ratio of 1: 1. went. Ferrite was used for the auxiliary anode.
- the current density was 25A / dm 2 at the peak of electric current amount in hydrochloric acid electrolysis of the aluminum plate was 63C / dm 2 as the total quantity of electricity when the anode. Then, water washing by spraying was performed.
- the aluminum plate 616 is conveyed as shown by the arrows in FIG.
- the aluminum plate 616 is charged (+) by the power supply electrode 620 in the power supply tank 612 in which the electrolytic solution 618 is stored.
- the aluminum plate 616 is conveyed upward by the roller 622 in the power supply tank 612, and the direction is changed downward by the nip roller 624.
- the aluminum plate 616 is conveyed toward the electrolytic treatment tank 614 in which the electrolytic solution 626 is stored, and by the roller 628. The direction is changed horizontally.
- the aluminum plate 616 is charged to ( ⁇ ) by the electrolytic electrode 630 to form an anodic oxide film on the surface thereof, and the aluminum plate 616 exiting the electrolytic treatment tank 614 is conveyed to a subsequent process.
- the direction changing means is constituted by the roller 622, the nip roller 624 and the roller 628, and the aluminum plate 616 is disposed between the power supply tank 612 and the electrolytic treatment tank 614 in the above-described rollers 622, 624 and 628. Thus, it is conveyed into a mountain shape and an inverted U shape.
- the feeding electrode 620 and the electrolytic electrode 630 are connected to a DC power source 634.
- (M) Hydrophilization treatment In order to ensure the hydrophilicity of the non-image area, a silicate treatment was performed by dipping at 50 ° C. for 7 seconds using a 2.5 mass% No. 3 sodium silicate aqueous solution. The adhesion amount of Si was 8.5 mg / m 2 . Then, water washing by spraying was performed.
- the small diameter hole portion includes a first small diameter hole portion and a second small diameter hole portion having different depths, and the deeper one is referred to as a first small diameter hole portion.
- the average value and the minimum value are shown as the barrier layer thickness.
- the average value is obtained by measuring the thickness of the anodized film from the bottom of the first small-diameter hole to the aluminum plate surface at 50 locations and arithmetically averaging them.
- the diameters of the micropores (large-diameter holes and small-diameter holes) existing in the range of 400 ⁇ 600 nm 2 were measured and averaged.
- the upper part of the anodized film was cut, and thereafter various diameters were obtained.
- the average depth of the small-diameter hole was measured by observing the cross section of the support (anodized film) with FE-SEM (50,000 times) and measuring the depth of 25 arbitrary micropores in the obtained image. The average value.
- “Communication density” means the density of small-diameter holes in the cross-section of the anodized film.
- “Surface area increase ratio” means a value calculated based on the following formula (A).
- Formula (A) Surface area increase ratio 1 + pore density ⁇ ( ⁇ ⁇ (surface layer average diameter / 2 + bottom average diameter / 2) ⁇ ((bottom average diameter / 2 ⁇ surface layer average diameter / 2) 2 + depth A 2 ) 1/2 + ⁇ ⁇ (Bottom average diameter / 2) 2 ⁇ ⁇ (surface layer average diameter / 2) 2 )
- the average depth of the second small diameter hole portion is shown on the left side
- the average depth of the first small diameter hole portion is shown on the right side.
- the density of the first small diameter hole is shown in parentheses together with the communication density of the small diameter hole. Further, the average diameter of the first small-diameter holes located from the bottom of the second small-diameter holes to the bottom of the first small-diameter holes was about 12 nm.
- Undercoat layer coating solution (1) having the following composition was applied so that the dry coating amount was 20 mg / m 2 to form an undercoat layer.
- Undercoat layer coating solution (1) ⁇ Undercoat layer compound (1) (the following structure) 0.18 g ⁇ Hydroxyethyliminodiacetic acid 0.05g ⁇ Surfactant (Emalex 710, manufactured by Nippon Emulsion Co., Ltd.) 0.03g ⁇ Water 28.0g
- an image recording layer coating solution (1) having the following composition was bar-coated and then oven-dried at 100 ° C. for 60 seconds to form an image recording layer having a dry coating amount of 1.0 g / m 2 .
- the image recording layer coating solution (1) was obtained by mixing and stirring the following photosensitive solution (1) and microgel solution (1) immediately before coating.
- Microgel solution (1) ⁇ Microgel (1) 2.640 g ⁇ Distilled water 2.425g
- microgel (1) As an oil phase component, 4.46 g of a polyfunctional isocyanate having the following structure (Mitsui Chemicals; 75 mass% ethyl acetate solution), trimethylolpropane (6 mol) and xylene diisocyanate (18 mol) were added to this, 10 g of an adduct (made by Mitsui Chemicals Polyurethane; 50% by mass ethyl acetate solution) to which polyoxyethylene (one mole, number of repeating oxyethylene units: 90) is added, pentaerythritol triacrylate (Nippon Kayaku Co., Ltd.) SR444) 3.15 g and Pionein A-41C (Takemoto Yushi Co., Ltd.) 0.1 g were dissolved in ethyl acetate 17 g.
- a polyfunctional isocyanate having the following structure (Mitsui Chemicals; 75 mass% ethyl acetate solution), trimethylolpropane (6 mol)
- aqueous phase component 40 g of a 4% by mass aqueous solution of polyvinyl alcohol (manufactured by Kuraray Co., Ltd., PVA-205) 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 measured by the light scattering method was 0.2 ⁇ m.
- a protective layer coating solution (1) having the following composition was applied with a bar, followed by oven drying at 120 ° C. for 60 seconds to form a protective layer having a dry coating amount of 0.15 g / m 2 and lithographic printing.
- An original plate 1 was prepared.
- thermoplastic fine particle polymer aqueous dispersion A 1000 ml four-necked flask was equipped with a stirrer, thermometer, dropping funnel, nitrogen inlet tube, reflux condenser, and nitrogen gas was introduced for deoxygenation, while polyethylene glycol methyl ether methacrylate (average of PEGMA, ethylene glycol) 20) 10 g, distilled water 200 g and n-propanol 200 g were added and heated until the internal temperature reached 70 ° C. Next, 10 g of premixed styrene (St), 80 g of acrylonitrile (AN) and 0.8 g of 2,2′-azobisisobutyronitrile were added dropwise over 1 hour.
- St premixed styrene
- AN acrylonitrile
- 2,2′-azobisisobutyronitrile 2,2′-azobisisobutyronitrile
- thermoplastic fine particle polymer aqueous dispersion having a mass ratio of PEGMA / St / AN 10/10/80 was obtained.
- the particle size distribution of the thermoplastic fine particle polymer had a maximum value at a volume average particle size of 150 nm.
- the particle size distribution is obtained by taking an electron micrograph of the fine particle polymer, measuring the total particle size of 5000 particles on the photograph, and logarithmic scale between 0 and the maximum value of the obtained particle size measurement value. And the frequency of appearance of each particle size was plotted and obtained.
- the particle size of spherical particles having the same particle area as that on the photograph was used as the particle size.
- 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.
- the support had a surface roughness Ra of 0.21 ⁇ m and an anodized film amount of 4 g / m 2 .
- aqueous recording liquid for image recording layer containing the following hydrophobic thermoplastic fine particle polymer, infrared absorber and polyacrylic acid is prepared, and after adjusting the pH to 3.6, it is applied onto a support and applied at 50 ° C. for 1 minute.
- An image recording layer was formed by drying to prepare a planographic printing plate precursor 3. The coating amount after drying of each component is shown below.
- thermoplastic fine particle polymer 0.7 g / m 2
- Infrared absorber IR-01 1.20 ⁇ 10 ⁇ 4 g / m 2
- Polyacrylic acid 0.09 g / m 2
- thermoplastic fine particle polymer used in the image recording layer coating solution are as follows.
- thermoplastic fine particle polymer styrene / acrylonitrile copolymer (molar ratio 50/50), Tg: 99 ° C., volume average particle diameter: 60 nm
- IR-01 Infrared absorber having the following structure
- polymer compounds described in Table F are as follows. ⁇ Polyvinylphosphonic acid (Mw: 30,000) Vinyl phosphonic acid / acrylamide copolymer (molar ratio 10/90) (Mw: 35,000) Polymer compound 1 (compound represented by the following formula P-1) (trade name: Polyphosmer PE-201, manufactured by DAP Corp., viscosity: 10 to 300 mPa ⁇ s, theoretical acid value: 311) Polymer compound 2 (compound represented by the following formula P-2) (Mw: 100,000) Polymer compound 3 (compound represented by the following formula P-3) (Mw: 50,000) ⁇ Sodium polyacrylate (Mw: 37,000)
- M 1 , M 2 , M 3 , M 4 , M 5 and M 6 each represent a hydrogen atom or a sodium atom.
- the number on the right side of the parenthesis represents the content (mol%) of the monomer unit with respect to all the monomer units of the polymer.
- Fine particles I Organic resin fine particles
- Organic resin fine particles prepared by the following method were used.
- ⁇ Organic resin fine particles> In a 1000 ml three-necked flask, 8 g of styrene, 1 g of divinylbenzene and 0.45 g of sodium dodecyl sulfate were weighed, dissolved in 28 g of distilled water, and stirred for 30 minutes at 65 ° C. under a nitrogen stream. To this solution, a solution prepared by dissolving 18.6 mg of 2,2′-azobis (2-amidinopropane) dihydrochloride in 2 g of distilled water was added and stirred at the same temperature for 6 hours.
- the reaction mixture was filtered through a glass filter to obtain an organic resin fine particle aqueous dispersion.
- the solid content concentration of the organic resin fine particle aqueous dispersion was 20% by mass, and the average particle diameter of the organic resin fine particles measured by the light scattering method was 87 nm.
- Microparticle II Microgel A microgel prepared by the following method was used. ⁇ Preparation of microgel> 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 alkylbenzene sulfonate (manufactured by Takemoto Yushi Co., Ltd., Pionin A-41C) 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
- aqueous phase component 40 g of a 4% by mass aqueous solution of polyvinyl alcohol (manufactured by Kuraray Co., Ltd., PVA-205) 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.
- the microgel solution thus obtained was diluted with distilled water to a solid content concentration of 15% by mass to prepare a microgel.
- the average particle size of the microgel measured by the light scattering method was 0.2 ⁇ m.
- Fine particles III Thermoplastic fine particles Thermoplastic fine particles prepared by the following method were used. ⁇ Preparation of thermoplastic fine particle aqueous dispersion> A 1,000 ml four-necked flask was equipped with a stirrer, thermometer, dropping funnel, nitrogen inlet tube, reflux condenser, and nitrogen gas was introduced for deoxygenation, while polyethylene glycol methyl ether methacrylate (PEGMA ethylene glycol) Average repeating unit number: 20) 10 g, distilled water 200 g and n-propanol 200 g were added and heated until the internal temperature reached 70 ° C.
- PEGMA ethylene glycol polyethylene glycol methyl ether methacrylate
- the particle size distribution of the thermoplastic fine particles had a maximum value at a volume average particle size of 150 nm.
- the particle size distribution is obtained by taking an electron micrograph of thermoplastic fine particles, measuring the total particle size of 5,000 particles on the photograph, and from 0 to the maximum value of the obtained particle size measurement value. Was divided into 50 on a logarithmic scale, and the frequency of appearance of each particle size was plotted. For non-spherical particles, the particle size of spherical particles having the same particle area as that on the photograph was used as the particle size.
- Fine particles IV inorganic fine particles Commercially available colloidal silica MP1040 (manufactured by Nissan Chemical Industries, Ltd./average particle size 0.1 ⁇ m / 40 mass% aqueous dispersion) was used.
- a method of cutting after coating the fine particle-containing coating solution was carried out as follows. Using 2NL04 manufactured by Hyojin Equipment Co., Ltd., which is a coating device related to the dispenser method, the transport speed is adjusted with a clearance of 0.3 mm and a liquid feeding amount of 5 ml / min, and a coating solution containing fine particles is applied to a predetermined solid content. It applied so that it might become. The application was performed on a region having a width of 10 mm at a position of 3 cm from both ends of two opposing sides of the planographic printing plate precursor.
- the application timing of the fine particle-containing coating solution is as follows (1) to (6).
- (1) The fine particle-containing coating solution was applied to the support and then dried at 85 ° C. for 30 seconds.
- the fine particle-containing coating solution was applied without drying and dried at 80 ° C. for 30 seconds.
- the fine particle-containing coating solution was applied without drying and dried at 150 ° C. for 20 seconds.
- the fine particle-containing coating solution was applied after drying at 80 ° C. for 30 seconds. Then, it was dried at 80 ° C. for 30 seconds.
- the fine particle-containing coating solution was applied without drying and dried at 150 ° C. for 1 minute.
- the fine particle-containing coating solution was applied after drying at 120 ° C. for 1 minute. Then, it was dried at 120 ° C. for 1 minute.
- the fine particle-containing coating solution, the lithographic printing plate precursor, and the coating time on the lithographic printing plate precursor were combined as shown in Table G, and the fine particle-containing coating solution was applied to the lithographic printing plate precursor.
- ⁇ Cutting> An end having a desired sag amount and sag width by adjusting the gap, biting amount and edge angle of the lithographic printing plate precursor using a rotary blade as shown in FIG. 2 and the upper cutting blade and lower cutting blade. It cut
- the center position of the coating region of the fine particle-containing coating solution was set as a cutting position, and two portions of the planographic printing plate precursor were cut.
- the sagging shape was measured by the following method, the sagging amount was 60 ⁇ m and the sagging width was 150 ⁇ m.
- ⁇ Cutting-Application of coating solution containing fine particles> After cutting, a method of applying the fine particle-containing coating solution was performed as follows.
- ⁇ Cutting> An end having a desired sag amount and sag width by adjusting the gap, biting amount and edge angle of the lithographic printing plate precursor using a rotary blade as shown in FIG. 2 and the upper cutting blade and lower cutting blade.
- the slit was continuously made so as to have the shape of the part.
- the sagging shape was measured by the following method, the sagging amount was 60 ⁇ m and the sagging width was 150 ⁇ m.
- Sagging shape measurement 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 stylus was moved from about 1 mm inside the lithographic printing plate precursor end to the end at a speed of 3 mm / sec, and the shape was measured.
- the coating method of the fine particle-containing coating solution is as follows (1) to (4).
- the area from the end of the lithographic printing plate precursor to 5 mm inside is adjusted by adjusting the conveyance speed so that the coating amount (solid content) is 0.8 g / m 2 under the conditions of a clearance of 6 mm and a discharge pressure of 0.05 MPa.
- the fine particle-containing coating solution was applied to the substrate, and then dried at 120 ° C. for 1 minute using a thermostat PH-201 manufactured by Espec Co., Ltd.
- the cloth containing the fine particle-containing coating solution is brought into contact with the end portion of the lithographic printing plate precursor, and the fine particles are formed in an area of 5 mm inward from the end portion of the lithographic printing plate precursor while sliding the cloth along the end portion. After the containing coating solution was applied, it was dried at 120 ° C. for 1 minute using a thermostat PH-201 manufactured by Espec Corporation.
- the cloth containing the fine particle-containing coating solution is brought into contact with the edge of the lithographic printing plate precursor, and the cloth is pressed from above to apply the fine particle-containing coating liquid to an area of 5 mm inward from the edge of the lithographic printing plate precursor. After coating, it was dried for 1 minute at 120 ° C.
- the fine particle-containing coating solution, the lithographic printing plate precursor and the coating method of the fine particle-containing coating solution were combined as shown in Table G, and the fine particle-containing coating solution was applied to the lithographic printing plate precursor.
- the film was immersed for 1 hour, the coating film components were removed, the support was removed, and a film removal solution A and a film removal solution B were obtained.
- Each of the membrane removal solution A and the membrane removal solution B was centrifuged at 11,000 rpm for 1 hour using a centrifuge (SRX-201, manufactured by Tommy Seiko Co., Ltd.), and then the supernatant was decanted. Removed. Furthermore, 300 ml of solvent A was added, and centrifugation and decantation of the supernatant were performed. Thereafter, 300 ml of methanol was added, and centrifugation and decantation of the supernatant were performed.
- the sediment was dried under reduced pressure (1 kPa, 60 ° C., 2 hours), and the weight was measured. From the weight of the sediment A obtained from the membrane removal solution A and the weight of the sediment B obtained from the membrane removal solution B, the content of fine particles per unit area contained in Sample A and Sample B (mg / m 2 ) was calculated.
- lithographic printing plate precursor produced as described above is exposed under the conditions of an external drum rotation speed of 1000 rpm, a laser output of 70%, and a resolution of 2,400 dpi using Fujifilm's Luxel PLASETTER T-6000III equipped with an infrared semiconductor laser. did.
- the exposed image includes a solid image and a 50% halftone dot chart.
- the exposed lithographic printing plate precursor is mounted on an offset rotary printing press, using Soiby KKST-S (Red) manufactured by Inktec Co., Ltd. as printing ink for newspapers, and Toyo ALKY manufactured by Toyo Ink Co., Ltd. as dampening water. , And printed at a speed of 100,000 sheets / hour.
- fine particle content difference means the content of fine particles per unit area in the region from the edge of the lithographic printing plate precursor to 5 mm and the content of fine particles per unit area in the region other than the above region. Means the difference. In Comparative Examples 1 to 21, since the fine particles according to the present invention are not applied to the end region of the lithographic printing plate precursor, the “fine particle content difference” is not measured. “Coating time” means the time when the fine particle-containing coating solution is applied to the position corresponding to the end region of the lithographic printing plate precursor in the step of forming the constituent layer of the lithographic printing plate precursor.
- Coating method refers to a method in which a lithographic printing plate precursor produced through the step of forming a constituent layer of the lithographic printing plate precursor is cut, and then a fine particle-containing coating solution is applied to the end region of the lithographic printing plate precursor. means.
- Example 72 when the planographic printing plate precursor was cut, the sagging amount and sagging width were adjusted as follows. That is, in Example 72, the sagging amount was 40 ⁇ m and the sagging width was 110 ⁇ m. In Example 73, the sagging amount was 35 ⁇ m and the sagging width was 80 ⁇ m. In Example 74, the sagging amount was 100 ⁇ m and the sagging width was 200 ⁇ m.
- the lithographic printing plate precursor according to the present invention containing specifically a large amount of fine particles in the end region is free from edge stains, and even when the lithographic printing plate precursor is stored in an overlapping manner. It can be seen that the transfer of the image recording layer is satisfactorily prevented. On the other hand, the lithographic printing plate precursor of Comparative Example is insufficient in at least one of edge smearing and image recording layer transfer.
- the lithographic printing plate precursor in which transfer of the image recording layer is prevented even when the lithographic printing plate precursor is stored in an overlapping manner without causing edge contamination, a method for producing the same, and a printing method using the same can be provided.
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Abstract
Description
(3)上記有機樹脂微粒子が、ミクロゲルである(2)に記載の平版印刷版原版。
(4)上記有機樹脂微粒子が、熱可塑性微粒子である(2)に記載の平版印刷版原版。
(5)上記微粒子が、無機微粒子である(1)に記載の平版印刷版原版。
(6)上記無機微粒子が、シリカ、アルミナ、酸化マグネシウム、酸化チタン、炭酸マグネシウム、アルギン酸カルシウム又はこれらの混合物である(5)に記載の平版印刷版原版。
(7)上記平版印刷版原版の端部が、ダレ量Xが35~150μm、ダレ幅Yが70~300μmのダレ形状を有する(1)~(6)のいずれか1項に記載の平版印刷版原版。
(8)上記端部から内側に5mmまでの画像記録層側版面の領域が、更に親水性化合物を含有する(1)~(7)のいずれか1項に記載の平版印刷版原版。
(9)上記親水性化合物が、支持体吸着性基を有する化合物である(8)に記載の平版印刷版原版。
(10)上記支持体吸着性基を有する化合物が、リン酸化合物又はホスホン酸化合物である(9)に記載の平版印刷版原版。
(11)上記リン酸化合物又は上記ホスホン酸化合物が、高分子化合物である(10)に記載の平版印刷版原版。
(12)上記画像記録層が、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)~(11)のいずれか1項に記載の平版印刷版原版。
(13)上記画像記録層が、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)~(11)のいずれか1項に記載の平版印刷版原版。
(14)上記画像記録層が、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)~(11)のいずれか1項に記載の平版印刷版原版。
(15)支持体上に画像記録層を有する平版印刷版原版の端部から内側に5mmまでの画像記録層側版面の領域に含まれる微粒子の単位面積当たりの含有量が、上記領域以外の領域における上記微粒子の単位面積当たりの含有量より、10mg/m2以上多い平版印刷版原版の製造方法であって、
(a)上記画像記録層を形成する画像記録層形成工程、
(b)上記微粒子を含有する塗布液を、a工程で形成される上記画像記録層の一部の領域と重なるように塗布する塗布工程、及び、
(c)上記塗布液を塗布した領域が、裁断後の平版印刷版原版の端部から内側に5mmまでの範囲にあるように裁断する裁断工程を、
上記支持体上に、a工程、b工程の順で行うか、又は、b工程、a工程の順で行い、その後c工程を行う平版印刷版原版の製造方法。
(16)a工程の前に、(d)下塗り層を形成する下塗り層形成工程を上記支持体上に行う(15)に記載の平版印刷版原版の製造方法。
(17)a工程の後、c工程の前に、(e)保護層を形成する保護層形成工程を上記画像記録層上に行う(15)又は(16)に記載の平版印刷版原版の製造方法。
(18)支持体上に画像記録層を有する平版印刷版原版の端部から内側に5mmまでの画像記録層側版面の領域に含まれる微粒子の単位面積当たりの含有量が、上記領域以外の領域における上記微粒子の単位面積当たりの含有量より、10mg/m2以上多い平版印刷版原版の製造方法であって、
(a)上記画像記録層を形成する画像記録層形成工程、及び
(f)上記微粒子を含有する塗布液を、上記平版印刷版原版の端部から内側に5mmまでの領域に塗布する塗布工程を、
上記支持体上に、a工程、f工程の順で行う平版印刷版原版の製造方法。
(19)a工程の前に、(d)下塗り層を形成する下塗り層形成工程を上記支持体上に行う(18)に記載の平版印刷版原版の製造方法。
(20)a工程の後、f工程の前に、(e)保護層を形成する保護層形成工程を上記画像記録層上に行う(18)又は(19)に記載の平版印刷版原版の製造方法。
(21)上記微粒子を含有する塗布液が、更に親水性化合物を含有する(15)~(20)のいずれか1項に記載の平版印刷版原版の製造方法。
(22)上記親水性化合物が、支持体吸着性基を有する化合物である(21)に記載の平版印刷版原版の製造方法。
(23)上記親水性化合物が、リン酸化合物又はホスホン酸化合物である(22)に記載の平版印刷版原版の製造方法。
(24)上記リン酸化合物又は上記ホスホン酸化合物が、高分子化合物である(23)に記載の平版印刷版原版の製造方法。
(25)(15)~(24)のいずれか1項に記載の製造方法により得られた平版印刷版原版。
(26)(1)~(14)及び(25)のいずれか1項に記載の平版印刷版原版を画像露光し、印刷インキ及び湿し水を供給して印刷機上で画像記録層の未露光部を除去し、印刷を行う印刷方法。
(27)上記平版印刷版原版の幅よりも広い印刷用紙を用いて印刷する(26)に記載の印刷方法。
本発明に係る平版印刷版原版は、支持体上に画像記録層を有する平版印刷版原版の端部から内側に5mmまでの画像記録層側版面の領域に含まれる微粒子の単位面積当たりの含有量が、上記領域以外の領域における上記微粒子の単位面積当たりの含有量より、10mg/m2以上多いことを特徴としている。
上記微粒子含有量の差は、好ましくは10~5000mg/m2、より好ましくは30~1000mg/m2、特に好ましくは50~500mg/m2である。
端部領域及びその他の領域おける単位面積当たりの微粒子の含有量は、以下のようにして定めることができる。
平版印刷版原版の端部領域及びその他の領域に該当する試料を準備し、各試料について支持体上の全塗布膜を水、有機溶剤又はこれらの混合物などの溶媒を用いて脱膜し、脱膜溶液に遠心分離操作を施して微粒子を分離し、微粒子の質量を測定し、質量を単位面積(m2)当たりに換算することにより端部領域及びその他の領域の単位面積当たりの微粒子の含有量を決定することができる。
脱膜溶液から微粒子を分離するには、通常の微粒子分離方法が用いられる。例えば、フィルタなどによりろ過する方法、遠心分離機によって微粒子を沈降させて濃縮する方法などが挙げられる。フィルタろ過の装置は、例えば、減圧あるいは加圧ろ過のような装置を用いることができる。好ましいフィルタとしては、ろ紙、ナノフィルタ、ウルトラフィルタなどを挙げることができる。遠心分離機は微粒子を沈降させることができる装置であればよく、例えば、汎用の装置の他にもスキミング機能(回転中に上澄み層を吸引し、系外に排出する機能)付きのものや、連続的に固形物を排出する連続遠心分離機などが挙げられる。
遠心分離条件は、遠心力(重力加速度の何倍の遠心加速度がかかるかを表す値)で50~50000が好ましく、100~40000がより好ましく、150~30000が特に好ましい。遠心分離時の温度は、使用する溶媒種によるが、-10~80℃が好ましく、-5~70℃がより好ましく、0~60℃が特に好ましい。
また、溶剤の除去工程としては、デカンテーションによる除去が一般的であるが、真空凍結乾燥により溶剤を昇華させて濃縮する方法、加熱ないし減圧による溶剤を乾燥させて濃縮する方法、これらを組合せた方法などを用いることもできる。
本発明に係る平版印刷版原版の端部領域に含有される微粒子は、平版印刷版原版中で微粒子状に存在する限り、有機微粒子及び無機微粒子のいずれでもよい。平版印刷版原版の構成層、例えば、下塗り層、画像記録層、保護層に含有されることが知られている各種の微粒子を用いてもよい。微粒子の存在により、機上現像型平版印刷版原版においては、湿し水の浸透性が向上し、機上現像が促進されることで、エッジ汚れが解消されると考えられる。
本発明に係る微粒子の中で、有機微粒子としては、有機樹脂微粒子、例えば、ミクロゲル(架橋ポリマー微粒子)、熱可塑性微粒子が好ましく用いられる。
ミクロゲルは、水性媒体に分散された反応性又は非反応性の樹脂粒子である。ミクロゲルは、その粒子中又は粒子表面に、好ましくは粒子表面に重合性基を有することにより、反応性ミクロゲルとした態様であってもよい。
熱可塑性微粒子としては、例えば、1992年1月のResearch 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号公報及び欧州特許第931647号公報などに記載の熱可塑性微粒子を好ましく挙げることができる。
本発明に係る微粒子の中で、無機微粒子としては、金属並びに金属化合物、例えば、酸化物、複合酸化物、水酸化物、炭酸塩、硫酸塩、ケイ酸塩、リン酸塩、有機酸塩、窒化物、炭化物、硫化物及びこれらの少なくとも2種以上の複合化物等が挙げられる。具体的には、シリカ、アルミナ、酸化マグネシウム、酸化チタン、炭酸マグネシウム、アルギン酸カルシウム、酸化ジルコン、酸化錫、チタン酸カリウム、チタン酸ストロンチウム、硼酸アルミニウム、硼酸マグネシウム、水酸化アルミニウム、水酸化マグネシウム、水酸化カルシウム、水酸化チタン、塩基性硫酸マグネシウム、炭酸カルシウム、硫酸カルシウム、硫酸マグネシウム、ケイ酸カルシウム、ケイ酸マグネシウム、リン酸カルシウム、窒化珪素、窒化チタン、窒化アルミ、炭化珪素、炭化チタン、硫化亜鉛及びこれらの少なくとも2種以上の複合化物等が挙げられる。好ましくは、シリカ、アルミナ、酸化マグネシウム、酸化チタン、炭酸マグネシウム、アルギン酸カルシウム又はこれらの混合物等が挙げられる。
微粒子の粒子径は、平均粒子径として、5μm以下が好ましく、0.005~3μmがより好ましく、0.01~2μmが特に好ましい。
粒子径の測定には、公知の方法を使用することができる。具体的には、レーザー回折・散乱法、動的光散乱法、静的光散乱法、動的画像法、静的画像法、画像解析法、電子顕微鏡法などが挙げられる。例えば、微粒子含有液を粒子濃度が0.1~1重量%になるように蒸留水などで希釈して、市販の平均粒子サイズ測定機(例えば、LA-910((株)堀場製作所製))で容易に測定することができる。更に、レーザードップラー効果を利用した動的光散乱法は、小サイズまで粒径測定が可能であり好ましい。また、平版印刷版原版においては、例えば、平版印刷版原版の切片を電子顕微鏡等で観察する方法や画像解析する方法などが容易に粒子サイズを測定できるため好ましい。
上記微粒子の粒子径は、レーザー回折・散乱法(測定装置:LA-910、(株)堀場製作所製)を用いて測定した数値である。
親水性化合物としては、水溶性の化合物が好ましい。水溶性化合物としては、20℃の水100gに0.5g以上溶解する化合物であれば、どのような化合物でも用いることができる。20℃の水100gに2g以上溶解する化合物がより好ましい。
リン酸化合物は、リン酸、その塩、そのエステルなどを含む。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、リン酸二水素ナトリウム、リン酸一水素ナトリウム、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。中でも、リン酸二水素ナトリウム、リン酸一水素ナトリウム、ヘキサメタリン酸ナトリウムが好ましく用いられる。
リン酸エステル基を有する高分子化合物としては、分子内にリン酸エステル基を有する単量体の1種以上からなる重合体、又は、リン酸エステル基を含む1種以上の単量体及びリン酸エステル基を含まない1種以上の単量体との共重合体、リン酸エステル基を有さない高分子にポリマー反応によりリン酸エステル基を導入した高分子などが挙げられる。
リン酸エステル基を有する単量体としては、モノ(2-メタクリロイルオキシエチル)アシッドホスフェート、モノ(2-メタクリロイルオキシポリオキシエチレングリコール)アシッドホスフェート、モノ(2-アクリロイルオキシエチル)アシッドホスフェート、3-クロロ-2-アシッドホスホオキシプロピルメタクリレート、アシッドホスホオキシポリオキシエチレングリコールモノメタクリレート、アシッドホスホオキシポリオキシプロピレングリコールメタクリレート、(メタ)アクリロイルオキシエチルアシッドホスフェート、(メタ)アクリロイルオキシプロピルアシッドホスフェート、(メタ)アクリロイルオキシ-2-ヒドロキシプロピルアシッドホスフェート、(メタ)アクリロイルオキシ-3-ヒドロキシプロピルアシッドホスフェート、(メタ)アクリロイルオキシ-3-クロロ-2-ヒドロキシプロピルアシッドホスフェート、アリルアルコールアシッドホスフェートなどが挙げられる。上記単量体の中でも、エッジ汚れ防止を助成する観点から、モノ(2-アクリロイルオキシエチル)アシッドホスフェートが好ましく用いられる。代表的な市販品としては、ライトエステルP-1M(共栄化学(株)製)、ホスマーPE(ユニケミカル(株)製)が挙げられる。
リン酸エステル基を有する高分子化合物の重量平均分子量は、5,000~1,000,000が好ましく、7,000~700,000がより好ましく、10,000~500,000が特に好ましい。
ホスホン酸化合物は、ホスホン酸、その塩、そのエステルなどを含む。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、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等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、ポリビニルホスホン酸が挙げられる。
ホスホン酸化合物として好ましい高分子化合物としては、ポリビニルホスホン酸、分子内にホスホン酸基又はホスホン酸モノエステル基を有する1種以上の単量体からなる重合体、ホスホン酸基又はホスホン酸モノエステル基を有する1種以上の単量体及びホスホン酸基又はホスホン酸モノエステル基を含まない1種以上の単量体との共重合体等が挙げられる。
ホスホン酸基を有する単量体としては、ビニルホスホン酸、エチルホスホン酸モノビニルエステル、アクリロイルアミノメチルホスホン酸、3-メタクリロイルオキシプロピルホスホン酸などが挙げられる。
上記共重合体における親水性基を有する単量体の親水性基としては、例えば、ヒドロキシ基、アルキレンオキシド構造、アミノ基、アンモニウム基、アミド基が挙げられ、中でも、ヒドロキシ基、アルキレンオキシド構造、アミド基が好ましく、炭素数2又は3のアルキレンオキシド単位を1~20個有するアルキレンオキシド構造がより好ましく、エチレンオキシド単位を2~10個有するポリエチレンオキシド構造が更に好ましい。例えば、2-ヒドロキシエチルアクリレート、エトキシジエチレングリコールアクリレート、メトキシトリエチレングリコールアクリレート、ポリ(オキシエチレン)メタクリレート、N-イソプロピルアクリルアミド、アクリルアミドなどが挙げられる。
ホスホン酸エステル基を有する高分子化合物の重量平均分子量は、5,000~1,000,000が好ましく、7,000~700,000がより好ましく、10,000~500,000が特に好ましい。
本発明に係る平版印刷版原版は、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、画像記録層の上に保護層を有してもよい。
平版印刷版原版の画像記録層は、その非画像部が、印刷機上で酸性~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A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、この塗布液を支持体上に直接又は下塗り層を介して、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、上記画像記録層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、上記画像記録層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C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、この塗布液を支持体上に直接又は下塗り層を介して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、必要により、下塗り層を設けることができる。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、必要により、保護層を設けることができる。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。
上述のとおり、本発明に係る平版印刷版原版は、端部領域が、その他の領域に比べて高い含有量の微粒子を含有する構成を有することが特徴である。この様な構成を有する平版印刷版原版が得られる限り、平版印刷版原版の製造方法は特に限定されるものではない。以下に、本発明に係る平版印刷版原版の製造方法を例示する。
即ち、平版印刷版原版の構成層を形成する工程において、微粒子を含有する塗布液を平版印刷版原版の端部領域に対応する位置に適用した後で、平版印刷版原版の端部領域が形成されるように裁断してもよいし、平版印刷版原版の構成層を形成する工程を経て製造された平版印刷版原版を裁断した後で、微粒子を含有する塗布液を平版印刷版原版の端部領域に適用してもよい。ここで、端部領域に対応する位置とは、裁断後の平版印刷版原版において、端部から内側に5mmまでの画像記録層側版面の領域を形成し得る位置を意味する。従って、端部領域に対応する位置は、平版印刷版原版の製造過程においては、平版印刷版原版の端付近の位置であっても、平版印刷版原版の中央付近の位置であってもよい。後者の場合、微粒子塗布領域に従って端部領域が形成されるように裁断することにより、端部領域を有する2枚の平版印刷版原版が得られる。
(a)上記画像記録層を形成する画像記録層形成工程、
(b)上記微粒子を含有する塗布液を、a工程で形成される上記画像記録層の一部の領域と重なるように塗布する塗布工程、及び、
(c)上記塗布液を塗布した領域が、裁断後の平版印刷版原版の端部から内側に5mmまでの画像記録層側版面の範囲にあるように裁断する裁断工程を、
上記支持体上に、a工程、b工程の順で行うか、又は、b工程、a工程の順で行い、その後c工程を行う平版印刷版原版の製造方法が挙げられる。
また、a工程の後、c工程の前に、(e)保護層を形成する保護層形成工程を上記画像記録層上に行ってもよい。
(a)上記画像記録層を形成する画像記録層形成工程、
(b)上記微粒子を含有する塗布液を、a工程で形成される上記画像記録層の一部の領域と重なるように塗布する塗布工程、
(c)上記塗布液を塗布した領域が、裁断後の平版印刷版原版の端部から内側に5mmまでの画像記録層側版面の範囲にあるように裁断する裁断工程、及び
(d)上記下塗り層を形成する下塗り層形成工程を、
上記支持体上に、b工程、d工程、a工程の順で行うか、d工程、b工程、a工程の順で行うか、又は、d工程、a工程、b工程の順で行い、その後c工程を行う平版印刷版原版の製造方法が挙げられる。
(a)上記画像記録層を形成する画像記録層形成工程、
(b)上記微粒子を含有する塗布液を、a工程で形成される上記画像記録層の一部の領域と重なるように塗布する塗布工程、
(c)上記塗布液を塗布した領域が、裁断後の平版印刷版原版の端部から内側に5mmまでの画像記録層側版面の範囲にあるように裁断する裁断工程、
(d)上記下塗り層を形成する下塗り層形成工程、及び、
(e)上記保護層を形成する保護層形成工程を、
上記支持体上に、b工程、d工程、a工程、e工程の順で行うか、d工程、b工程、a工程、e工程の順で行うか、d工程、a工程、b工程、e工程の順で行うか、又は、d工程、a工程、e工程、b工程の順で行い、その後c工程を行う平版印刷版原版の製造方法が挙げられる。
(a)上記画像記録層を形成する画像記録層形成工程、及び
(f)上記微粒子を含有する塗布液を、上記平版印刷版原版の端部から内側に5mmまでの領域に塗布する塗布工程を、
上記支持体上に、a工程、f工程の順で行う平版印刷版原版の製造方法が挙げられる。
また、a工程の後、f工程の前に、(e)保護層を形成する保護層形成工程を上記画像記録層上に行ってもよい。
(a)上記画像記録層を形成する画像記録層形成工程、
(f)上記微粒子を含有する塗布液を、上記平版印刷版原版の端部から内側に5mmまでの領域に塗布する塗布工程、及び
(d)上記下塗り層を形成する下塗り層形成工程を、
上記支持体上に、d工程、a工程、f工程の順で行う平版印刷版原版の製造方法が挙げられる。
(a)上記画像記録層を形成する画像記録層形成工程、
(f)上記微粒子を含有する塗布液を、上記平版印刷版原版の端部から内側に5mmまでの領域に塗布する塗布工程、
(d)上記下塗り層を形成する下塗り層形成工程、及び、
(e)上記保護層を形成する保護層形成工程を、
上記支持体上に、d工程、a工程、e工程、f工程の順で行う平版印刷版原版の製造方法が挙げられる。
微粒子含有塗布液は、先に記載した微粒子を含有する塗布液である。微粒子含有塗布液は、主として水からなる媒体中に微粒子が分散した水系分散液の形態を有する。
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。
微粒子含有塗布液に用いられる界面活性剤としては、アニオン性界面活性剤、非イオン性界面活性剤、カチオン性界面活性剤、両性界面活性剤が挙げられる。アニオン性界面活性剤、非イオン性界面活性剤が好ましい。界面活性剤は、微粒子の分散安定性を向上させ、微粒子の凝集、沈降を防止する効果がある。
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。
有機溶剤は、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。
微粒子含有塗布液は、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。
微粒子含有塗布液は、微粒子及び必要に応じて使用する添加剤等の成分を一緒に溶媒、例えば、水(蒸留水、イオン交換水、脱塩水など)中で混合分散して調製してもよいし、予め、微粒子を溶媒に分散した微粒子分散液を調製後、これにその他の添加剤等を添加混合して調製してもよい。
微粒子含有塗布液の粘度は、25℃において、好ましくは0.5~1000mPa・s、より好ましくは1~100mPa・sである。粘度が上記範囲内であると、ビード破断が起きにくくなり、塗布開始時の塗り付けが良好となる点で好ましい。
微粒子含有塗布液の表面張力は、25℃において、好ましくは25~70mN/m、より好ましくは40~65mN/mであることがより好ましい。表面張力が上記範囲内であると、塗布幅の制御がしやすく、ビード破断が起きにくくなる点で好ましい。
微粒子含有塗布液は、上記のように、平版印刷版原版の製造過程において、端部領域に対応する位置に塗布される。塗布幅については、端部又は端部に相当する位置から5mmまでの領域が好ましく、3mmまでの領域がより好ましい。
微粒子含有塗布液の塗布には、ダイコート法、ディップコート法、エアーナイフコート法、カーテンコート法、ローラーコート法、ワイヤーバーコート法、グラビアコート法、スライドコート法、インクジェット法、ディスペンサー法、スプレー法等の公知の方法を利用することができる。塗布液を特定の位置に塗布する観点からは、インクジェット法又はディスペンサー法が好ましい。
裁断後に微粒子含有塗布液を塗布する態様では、上記塗布方法に加えて、微粒子含有塗布液を含浸させた布やモルトンロールを用いる塗布方法も利用できる。
微粒子含有塗布液の塗布量は、乾燥後の固形分として、0.01~6.0g/m2が好ましく、0.03~3.0g/m2がより好ましく、0.05~2.0g/m2が特に好ましい。
乾燥は、オーブンを用いる、乾燥風を吹き付けるなどにより行うことができる。乾燥温度は60~220℃が好ましく、80~180℃がより好ましい。
平版印刷版原版は、上記のように、平版印刷版原版の製造過程において、裁断される。裁断は、公知の裁断方法を利用して行うことができる。好ましくは、特開平8-58257号公報、特開平9-211843号公報、特開平10-100556号公報、特開平11-52579号公報に記載の方法が使用できる。
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以上が好ましく、40μm以上がより好ましい。ダレ量の上限は、端部表面状態の悪化による機上現像性の劣化を防止する観点から150μmが好ましい。機上現像性が劣化すると残存する感光層にインキが付着しエッジ汚れ発生の原因となる。ダレ量が35μmを下回ると、端部に付着したインキがブランケットに転写しやすくなりエッジ汚れ発生の原因となる場合がある。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70~300μmの範囲が適当であり、80~250μm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。
平版印刷版原版の画像露光は、通常の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。
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、画像露光された平版印刷版原版に、印刷機上で、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。
従って、新聞印刷用に用いられる機上現像型平版印刷版原版として、本発明に係る平版印刷版原版は特にその優れた特性を発揮する。
〔平版印刷版原版1の作製〕
<支持体の作製>
厚さ0.3mmの表Aに示す組成のアルミニウム合金板に対し、下記(a)~(m)の処理を施し、支持体を作製した。なお、全ての処理工程の間には水洗処理を施し、水洗処理の後にはニップローラで液切りを行った。
図3に示すような装置を使って、パミスの懸濁液(比重1.1g/cm3)を研磨スラリー液としてアルミニウム板の表面に供給しながら、回転する束植ブラシにより機械的粗面化処理を行った。図3において、41はアルミニウム板、42及び44はローラ状ブラシ(本実施例においては、束植ブラシ)、43は研磨スラリー液、45、46、47及び48は支持ローラである。
アルミニウム板に、カセイソーダ濃度26質量%、アルミニウムイオン濃度6.5質量%のカセイソーダ水溶液を、温度70℃でスプレー管により吹き付けてエッチング処理を行った。その後、スプレーによる水洗を行った。アルミニウム溶解量は、10g/m2であった。
次に、硝酸水溶液中でデスマット処理を行った。デスマット処理に用いた硝酸水溶液は、次工程の電気化学的粗面化に用いた硝酸電解液を用いた。液温は35℃であった。デスマット液をスプレーにて吹き付けて3秒間デスマット処理を行った。
60Hzの交流電圧を用いて連続的に電気化学的な粗面化処理を行った。電解液は、温度35℃、硝酸10.4g/Lの水溶液に硝酸アルミニウムを添加してアルミニウムイオン濃度を4.5g/Lに調整した電解液を用いた。交流電源波形は電流値がゼロからピークに達するまでの時間tpが0.8msec、duty比1:1、台形の矩形波交流を用いて、カーボン電極を対極として電気化学的な粗面化処理を行った。補助アノードにはフェライトを用いた。電解槽は図4に示すものを使用した。図4において、アルミニウム板Wは主電解槽50中に浸漬して配置されたラジアルドラムローラ52に巻装され、搬送過程で交流電源51に接続する主極53a、53bにより電解処理された。電解液55は電解液供給口54からスリット56を通じてラジアルドラムローラ52と主極53a、53bとの間の電解液通路57に供給された。主電解槽50で処理されたアルミニウム板Wは次いで補助陽極槽60で電解処理された。この補助陽極槽60には補助陽極58がアルミニウム板Wと対向配置されており、電解液55が補助陽極58とアルミニウム板Wとの間の空間を流れるように供給された。電流密度は電流のピーク値で30A/dm2、補助陽極には電源から流れる電流の5%を分流させた。電気量はアルミニウム板が陽極時の電気量の総和で185C/dm2であった。その後、スプレーによる水洗を行った。
アルミニウム板に、カセイソーダ濃度5質量%、アルミニウムイオン濃度0.5質量%のカセイソーダ水溶液を、温度50℃でスプレー管により吹き付けてエッチング処理を行った。その後、スプレーによる水洗を行った。アルミニウム溶解量は、0.5g/m2であった。
次に、硫酸水溶液中でデスマット処理を行った。デスマット処理には、硫酸濃度170g/L、アルミニウムイオン濃度5g/Lの硫酸水溶液を用いた。液温は60℃であった。デスマット液をスプレーにて吹き付けて3秒間デスマット処理を行った。
60Hzの交流電圧を用いて連続的に電気化学的な粗面化処理を行った。電解液は、液温35℃、塩酸6.2g/Lの水溶液に塩化アルミニウムを添加してアルミニウムイオン濃度を4.5g/Lに調整した電解液を用いた。交流電源波形は電流値がゼロからピークに達するまでの時間tpが0.8msec、duty比1:1、台形の矩形波交流を用いて、カーボン電極を対極として電気化学的な粗面化処理を行った。補助アノードにはフェライトを用いた。電解槽は図4に示すものを使用した。電流密度は電流のピーク値で25A/dm2であり、塩酸電解における電気量はアルミニウム板が陽極時の電気量の総和で63C/dm2であった。その後、スプレーによる水洗を行った。
アルミニウム板に、カセイソーダ濃度5質量%、アルミニウムイオン濃度0.5質量%のカセイソーダ水溶液を、温度50℃でスプレー管により吹き付けてエッチング処理を行った。その後、スプレーによる水洗を行った。アルミニウム溶解量は、0.1g/m2であった。
次に、硫酸水溶液中でデスマット処理を行った。陽極酸化処理工程で使用する硫酸水溶液(硫酸170g/L水溶液中にアルミニウムイオン5g/Lを含有)を用い、液温35℃で4秒間デスマット処理を行った。デスマット液はスプレーにて吹き付けて3秒間デスマット処理を行った。
図5に示す構造の直流電解による陽極酸化装置を用いて第1段階の陽極酸化処理を行った。表Bに示す条件にて陽極酸化処理を行い、所定の皮膜厚の陽極酸化皮膜を形成した。電解液には、表Bに示す成分を含む水溶液を用いた。表B~Dにおいて、「成分濃度」は、「液成分」欄に記載の各成分の含有濃度(g/l)を表す。
図5に示す構造の直流電解による陽極酸化装置を用いて第2段階の陽極酸化処理を行った。表Cに示す条件にて陽極酸化処理を行い、所定の皮膜厚の陽極酸化皮膜を形成した。電解液には、表Cに示す成分を含む水溶液を用いた。
図5に示す構造の直流電解による陽極酸化装置を用いて第3段階の陽極酸化処理を行った。表Dに示す条件にて陽極酸化処理を行い、所定の皮膜厚の陽極酸化皮膜を形成した。電解液には、表Dに示す成分を含む水溶液を用いた。
非画像部の親水性を確保するため、2.5質量%3号ケイ酸ソーダ水溶液を用いて50℃で7秒間ディップしてシリケート処理を施した。Siの付着量は8.5mg/m2であった。その後、スプレーによる水洗を行った。
大径孔部の平均深さは、支持体(陽極酸化皮膜)の断面を倍率50万倍のFE-TEMで観察し、得られた画像において、任意のマイクロポアの表面から連通位置までの距離を60個(N=60)測定し、それらを平均した値である。また、小径孔部の平均深さは、支持体(陽極酸化皮膜)の断面をFE-SEMで観察し(5万倍)、得られた画像において、任意のマイクロポア25個の深さを測定し、平均した値である。
式(A)
表面積増加倍率 = 1+ポア密度×(π×(表層平均径/2+底部平均径/2)×((底部平均径/2-表層平均径/2)2+深さA2)1/2+π×(底部平均径/2)2-π×(表層平均径/2)2)
小径孔部の「平均深さ(nm)」欄において、第2の小径孔部の平均深さを左側に、第1の小径孔部の平均深さを右側に示す。表E中の小径孔部の「連通部密度」欄において、小径孔部の連通部密度と共に、第1の小径孔部の密度をカッコ書き中に示す。
また、第2の小径孔部の底部から第1の小径孔部の底部までに位置する第1の小径孔部の平均径は、12nm程度であった。
支持体上に、下記組成の下塗り層塗布液(1)を乾燥塗布量が20mg/m2になるよう塗布して、下塗り層を形成した。
(下塗り層塗布液(1))
・下塗り層用化合物(1)(下記構造) 0.18g
・ヒドロキシエチルイミノ二酢酸 0.05g
・界面活性剤(エマレックス710、日本エマルジョン(株)製)
0.03g
・水 28.0g
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℃で60秒オーブン乾燥し、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撹拌することにより得た。
(感光液(1))
・バインダーポリマー(1)(下記構造) 0.240g
(Mw:55,000、n:2(EO単位数))
・赤外線吸収剤(1)(下記構造) 0.020g
・ボレート化合物(1) 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)
・アニオン性界面活性剤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)
(Mw:50,000、還元比粘度 45ml/g)
・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、下記構造の多官能イソシアナート(三井化学製;75質量%酢酸エチル溶液)4.46g、トリメチロールプロパン(6モル)とキシレンジイソシアナート(18モル)を付加させ、これにメチル片末端ポリオキシエチレン(1モル、オキシエチレン単位の繰り返し数:90)を付加させた付加体(三井化学ポリウレタン製;50質量%酢酸エチル溶液)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((株)クラレ製、PVA-205)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)を作製した。光散乱法により測定したミクロゲルの平均粒径は0.2μmであった。
画像記録層上に、下記組成の保護層用塗布液(1)をバー塗布した後、120℃で60秒オーブン乾燥し、乾燥塗布量0.15g/m2の保護層を形成して平版印刷版原版1を作製した。
・無機層状化合物分散液(1)(下記) 1.5g
・親水性ポリマー(1)(下記構造、Mw:3万)(固形分)0.03g
・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、日本エマルジョン(株)製)
(下記構造)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体積平均粒子径(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。
<画像記録層の形成>
平版印刷版原版1の作製に用いた下塗り層を有する支持体の下塗り層上に、下記組成の画像記録層塗布液(2)をバー塗布した後、70℃で60秒オーブン乾燥し、乾燥塗布量0.6g/m2の画像記録層を形成した。
・熱可塑性微粒子ポリマー水分散液 (下記) 20.0g
・赤外線吸収剤(2)(下記構造) 0.2g
・重合開始剤 0.4g
Irgacure250(チバスペシャリティケミカルズ製)
・重合開始剤(2)(下記構造) 0.15g
・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 2.5g
Acrylics社製)
・アニオン性界面活性剤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数: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ポリマー化は98%以上進行しており、質量比でPEGMA/St/AN=10/10/80の熱可塑性微粒子ポリマー水分散液が得られた。この熱可塑性微粒子ポリマーの粒径分布は、体積平均粒子径150nmに極大値を有していた。
<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、乾燥して支持体を作製した。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。
下記疎水性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水系塗布液を調製し、pHを3.6に調整した後、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3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: 1.20×10-4g/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
<微粒子含有塗布液の調製>
下記表Fに記載した成分を純水に加えて撹拌し、微粒子含有塗布液A~Z及びa~bを調製した。化合物名の右に記載した、括弧内の数字は当該成分の質量%濃度を表す。なお、「微粒子含有塗布液a」及び「微粒子含有塗布液b」は、比較用の塗布液であり、微粒子を含有していない。
・ポリビニルホスホン酸(Mw:30,000)
・ビニルホスホン酸/アクリルアミド共重合体(モル比10/90)(Mw:35,000)
・高分子化合物1(下記式P-1で表される化合物)(商品名:ポリホスマー PE-201、DAP(株)製、粘度:10~300mPa・s、理論酸価:311)
・高分子化合物2(下記式P-2で表される化合物)(Mw:100,000)
・高分子化合物3(下記式P-3で表される化合物)(Mw:50,000)
・ポリアクリル酸ナトリウム(Mw:37,000)
微粒子I:有機樹脂微粒子
以下の方法で作製した有機樹脂微粒子を使用した。
<有機樹脂微粒子>
1000mlの三口フラスコに、スチレン8g、ジビニルベンゼン1g、ドデシル硫酸ナトリウム0.45gを秤取り、蒸留水28gに溶かし、65℃、窒素気流下にて30分間攪拌した。この溶液に、2,2’-アゾビス(2-アミジノプロパン)ジハイドロクロライド18.6mgを蒸留水2gに溶かした溶液を加え、同温度で6時間攪拌した。反応終了後、反応混合物をグラスフィルターで濾過し、有機樹脂微粒子水分散液を得た。有機樹脂微粒子水分散液の固形分濃度は20質量%であり、光散乱法により測定した有機樹脂微粒子の平均粒径は87nmであった。
以下の方法で作製したミクロゲルを使用した。
<ミクロゲルの作製>
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及びアルキルベンゼンスルホン酸塩(竹本油脂(株)製、パイオニンA-41C)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((株)クラレ製、PVA-205)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分撹拌後、50℃で3時間撹拌した。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、ミクロゲルを作製した。光散乱法により測定したミクロゲルの平均粒径は0.2μmであった。
以下の方法で作製した熱可塑性微粒子を使用した。
<熱可塑性微粒子水分散液の作製>
1,000ml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繰返し単位数: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ポリマー化は98%以上進行しており、質量比でPEGMA/St/AN=10/10/80の熱可塑性微粒子水分散液が得られた。この熱可塑性微粒子の粒径分布は、体積平均粒子径150nmに極大値を有していた。
市販のコロイダルシリカMP1040(日産化学工業(株)製/平均粒径0.1μm/40質量%水分散液)を使用した。
微粒子含有塗布液を塗布後、裁断を行う方法を以下のように実施した。
ディスペンサー法に係る塗布装置である、兵神装備(株)製2NL04を使用し、クリアランス0.3mm、送液量5ml/分で搬送速度を調整し、微粒子含有塗布液を所定の固形分塗布量になるように塗布した。
塗布は、平版印刷版原版の対向する2辺の両端部からそれぞれ3cmの位置において幅10mmの領域に行った。
微粒子含有塗布液の塗布時期は、下記(1)~(6)のとおりである。
(1)支持体に微粒子含有塗布液を塗布後、85℃で30秒間乾燥させた。
(2)下塗り層の塗布後、乾燥させないまま微粒子含有塗布液を塗布、80℃で30秒間乾燥させた。
(3)下塗り層の塗布後、乾燥させないまま微粒子含有塗布液を塗布、150℃で20秒間乾燥させた。
(4)下塗り層の塗布後、80℃で30秒間乾燥してから微粒子含有塗布液を塗布した。その後、80℃で30秒間乾燥させた。
(5)保護層の塗布後(保護層の形成を行わない場合は、画像記録層の塗布後)、乾燥させないまま微粒子含有塗布液を塗布、150℃で1分間乾燥させた。
(6)保護層の塗布後(保護層の形成を行わない場合は、画像記録層の塗布後)、120℃で1分間乾燥してから微粒子含有塗布液を塗布した。その後、120℃で1分間乾燥させた。
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裁断した。上記の裁断条件により、微粒子含有塗布液の塗布領域の中央の位置を裁断位置とし、平版印刷版原版の2箇所を裁断した。下記の方法でダレ形状の測定を行ったところ、ダレ量は60μm、ダレ幅は150μmであった。
裁断後、微粒子含有塗布液の塗布を行う方法を以下のように実施した。
<裁断>
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。下記の方法でダレ形状の測定を行ったところ、ダレ量は60μm、ダレ幅は150μmであった。
微粒子含有塗布液の塗布方法は、下記(1)~(4)のとおりである。
(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内側に5mmまでの領域に微粒子含有塗布液を塗布した後、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。
(2)微粒子含有塗布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内側に5mmまでの領域に微粒子含有塗布液を塗布した後、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。
(3)微粒子含有塗布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内側に5mmまでの領域に微粒子含有塗布液を塗布した後、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。
(4)微粒子含有塗布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内側に5mmまでの領域に微粒子含有塗布液を塗布した後、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。
対向する長辺2辺がエッジ処理された平版印刷版原版(400mm×1100mm)25枚から、エッジ処理した端部を1辺とする5mm×1100mmの長方形を50枚切断し、サンプルAとした。一方、エッジ処理した端部を切断した残りの平版印刷版原版(390mm×1100mm)1枚を、サンプルBとした。
サンプルA及びサンプルBを5mm×1cm角に更に切断し、メチルエチルケトン(MEK)/プロピレングリコールモノメチルエーテル/メタノール/水の混合溶媒(3/6/1/1(質量比))(溶媒A)360mlに1時間浸漬、塗布膜成分を脱膜し、支持体を取除いて、脱膜溶液A及び脱膜溶液Bを得た。
脱膜溶液A及び脱膜溶液Bのそれぞれについて、遠心分離機(SRX-201、(株)トミー精工製)を用いて、11,000rpmで1時間遠心分離を行った後、上澄み液をデカンテーションで除去した。更に、溶媒Aを300ml添加し、遠心分離及び上澄み液のデカンテーションを行った。その後、メタノールを300ml添加し、遠心分離及び上澄み液のデカンテーションを行った。沈降物を減圧乾燥(1kPa、60℃、2時間)し、重量を測定した。脱膜溶液Aから得られた沈降物Aの重量と脱膜溶液Bから得られた沈降物Bの重量から、サンプルA及びサンプルBに含まれる単位面積当たりの微粒子含有量(mg/m2)を計算により求めた。
上記のようにして作製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2,400dpi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。
露光後の平版印刷版原版を、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 ソイビーKKST-S(紅)、湿し水として東洋インキ(株)製東洋ALKYを用い、100,000枚/時のスピードで印刷した。
<エッジ汚れ防止性能の評価>
上記印刷過程において、1,000枚目の印刷物をサンプリングし、エッジ部の線状汚れの程度を目視で観察し、下記の基準で評価した。5~3が許容水準である。
5:汚れは全く認められない。
4:5と3の中間レベル。
3:汚れがうっすらと認められる。
2:3と1の中間レベル
1:汚れがはっきりと認められる。
作製した平版印刷版原版を2枚重ね、万力を用いて版面に対して20(kg/cm2)の圧力をかけた状態で、25℃1日間保管した後、平版印刷版原版の端部処理領域と接触していたもう一方の平版印刷版原版の裏面を目視で観察し、裏面への転写物を下記の基準で評価した。5~4が許容水準である。
5:転写物は全く認められない。
4:転写物がうっすら見える。
3:転写物が連続する線としてうっすら見える。
2:転写物が連続する線として見える。
1:転写物が連続する線としてはっきり見える。
本出願は、2014年9月26日出願の日本特許出願(特願2014-197264)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
X ダレ量
Y ダレ幅
B 画像記録層と支持体との境界
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
41 アルミニウム板
42、44 ローラ状ブラシ
43 研磨スラリー液
45、46、47、48 支持ローラ
50 主電解槽
51 交流電源
52 ラジアルドラムローラ
53a,53b 主極
54 電解液供給口
55 電解液
56 スリット
58 補助陽極
60 補助陽極槽
W アルミニウム板
610 陽極酸化処理装置
612 給電槽
614 電解処理槽
616 アルミニウム板
618、626 電解液
620 給電電極
622、628 ローラ
624 ニップローラ
630 電解電極
632 槽壁
634 直流電源
Claims (27)
- 支持体上に画像記録層を有する平版印刷版原版の端部から内側に5mmまでの画像記録層側版面の領域に含まれる微粒子の単位面積当たりの含有量が、前記領域以外の領域における前記微粒子の単位面積当たりの含有量より、10mg/m2以上多い平版印刷版原版。
- 前記微粒子が、有機樹脂微粒子である請求項1に記載の平版印刷版原版。
- 前記有機樹脂微粒子が、ミクロゲルである請求項2に記載の平版印刷版原版。
- 前記有機樹脂微粒子が、熱可塑性微粒子である請求項2に記載の平版印刷版原版。
- 前記微粒子が、無機微粒子である請求項1に記載の平版印刷版原版。
- 前記無機微粒子が、シリカ、アルミナ、酸化マグネシウム、酸化チタン、炭酸マグネシウム、アルギン酸カルシウム又はこれらの混合物である請求項5に記載の平版印刷版原版。
- 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70~300μmのダレ形状を有する請求項1~6のいずれか1項に記載の平版印刷版原版。
- 前記端部から内側に5mmまでの画像記録層側版面の領域が、更に親水性化合物を含有する請求項1~7のいずれか1項に記載の平版印刷版原版。
- 前記親水性化合物が、支持体吸着性基を有する化合物である請求項8に記載の平版印刷版原版。
- 前記支持体吸着性基を有する化合物が、リン酸化合物又はホスホン酸化合物である請求項9に記載の平版印刷版原版。
- 前記リン酸化合物又は前記ホスホン酸化合物が、高分子化合物である請求項10に記載の平版印刷版原版。
- 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1~11のいずれか1項に記載の平版印刷版原版。
- 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1~11のいずれか1項に記載の平版印刷版原版。
- 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1~11のいずれか1項に記載の平版印刷版原版。
- 支持体上に画像記録層を有する平版印刷版原版の端部から内側に5mmまでの画像記録層側版面の領域に含まれる微粒子の単位面積当たりの含有量が、前記領域以外の領域における前記微粒子の単位面積当たりの含有量より、10mg/m2以上多い平版印刷版原版の製造方法であって、
(a)前記画像記録層を形成する画像記録層形成工程、
(b)前記微粒子を含有する塗布液を、a工程で形成される前記画像記録層の一部の領域と重なるように塗布する塗布工程、及び、
(c)前記塗布液を塗布した領域が、裁断後の平版印刷版原版の端部から内側に5mmまでの範囲にあるように裁断する裁断工程を、
前記支持体上に、a工程、b工程の順で行うか、又は、b工程、a工程の順で行い、その後c工程を行う平版印刷版原版の製造方法。 - a工程の前に、(d)下塗り層を形成する下塗り層形成工程を前記支持体上に行う請求項15に記載の平版印刷版原版の製造方法。
- a工程の後、c工程の前に、(e)保護層を形成する保護層形成工程を前記画像記録層上に行う請求項15又は16に記載の平版印刷版原版の製造方法。
- 支持体上に画像記録層を有する平版印刷版原版の端部から内側に5mmまでの画像記録層側版面の領域に含まれる微粒子の単位面積当たりの含有量が、前記領域以外の領域における前記微粒子の単位面積当たりの含有量より、10mg/m2以上多い平版印刷版原版の製造方法であって、
(a)前記画像記録層を形成する画像記録層形成工程、及び
(f)前記微粒子を含有する塗布液を、前記平版印刷版原版の端部から内側に5mmまでの領域に塗布する塗布工程を、
前記支持体上に、a工程、f工程の順で行う平版印刷版原版の製造方法。 - a工程の前に、(d)下塗り層を形成する下塗り層形成工程を前記支持体上に行う請求項18に記載の平版印刷版原版の製造方法。
- a工程の後、f工程の前に、(e)保護層を形成する保護層形成工程を前記画像記録層上に行う請求項18又は19に記載の平版印刷版原版の製造方法。
- 前記微粒子を含有する塗布液が、更に親水性化合物を含有する請求項15~20のいずれか1項に記載の平版印刷版原版の製造方法。
- 前記親水性化合物が、支持体吸着性基を有する化合物である請求項21に記載の平版印刷版原版の製造方法。
- 前記親水性化合物が、リン酸化合物又はホスホン酸化合物である請求項22に記載の平版印刷版原版の製造方法。
- 前記リン酸化合物又は前記ホスホン酸化合物が、高分子化合物である請求項23に記載の平版印刷版原版の製造方法。
- 請求項15~24のいずれか1項に記載の製造方法により得られた平版印刷版原版。
- 請求項1~14及び25のいずれか1項に記載の平版印刷版原版を画像露光し、印刷インキ及び湿し水を供給して印刷機上で画像記録層の未露光部を除去し、印刷を行う印刷方法。
- 前記平版印刷版原版の幅よりも広い印刷用紙を用いて印刷する請求項26に記載の印刷方法。
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EP15844261.6A EP3199367B1 (en) | 2014-09-26 | 2015-08-14 | Lithographic printing plate precursor, process for producing same, and printing method using same |
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CN201580052393.3A CN106687300B (zh) | 2014-09-26 | 2015-08-14 | 平版印刷版原版、平板印刷版原版的制造方法及利用平版印刷版的印刷方法 |
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WO2018230412A1 (ja) * | 2017-06-12 | 2018-12-20 | 富士フイルム株式会社 | 平版印刷版原版、平版印刷版の製版方法、有機ポリマー粒子、及び、感光性樹脂組成物 |
US20200223216A1 (en) * | 2017-09-29 | 2020-07-16 | Fujifilm Corporation | Lithographic printing plate precursor and method of producing lithographic printing plate |
US11458757B2 (en) * | 2017-08-31 | 2022-10-04 | Fujifilm Corporation | Lithographic printing plate precursor and method of producing lithographic printing plate |
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EP3251868B1 (en) * | 2015-01-29 | 2020-01-15 | FUJIFILM Corporation | Lithographic printing plate master, manufacturing method therefor, and printing method using same |
JP6791680B2 (ja) * | 2016-08-09 | 2020-11-25 | 株式会社フジミインコーポレーテッド | 表面処理組成物およびこれを用いた洗浄方法 |
CN111051073B (zh) * | 2017-08-30 | 2021-06-29 | 富士胶片株式会社 | 机上显影型平版印刷版原版及平版印刷版的制作方法 |
JP6924265B2 (ja) * | 2017-08-31 | 2021-08-25 | 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 |
US11686208B2 (en) | 2020-02-06 | 2023-06-27 | Rolls-Royce Corporation | Abrasive coating for high-temperature mechanical systems |
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US11567404B2 (en) | 2017-06-12 | 2023-01-31 | Fujifilm Corporation | Lithographic printing plate precursor, method for making lithographic printing plate, organic polymer particle, and photosensitive resin composition |
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US20200223216A1 (en) * | 2017-09-29 | 2020-07-16 | Fujifilm Corporation | Lithographic printing plate precursor and method of producing lithographic printing plate |
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