WO2010116808A1 - 平版印刷版原版 - Google Patents
平版印刷版原版 Download PDFInfo
- Publication number
- WO2010116808A1 WO2010116808A1 PCT/JP2010/052891 JP2010052891W WO2010116808A1 WO 2010116808 A1 WO2010116808 A1 WO 2010116808A1 JP 2010052891 W JP2010052891 W JP 2010052891W WO 2010116808 A1 WO2010116808 A1 WO 2010116808A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- printing plate
- lithographic printing
- plate precursor
- image recording
- Prior art date
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C1/00—Forme preparation
- B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
- B41C1/1008—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
-
- 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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
-
- 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
- G03F7/092—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers characterised by backside coating or layers, by lubricating-slip layers or means, by oxygen barrier layers or by stripping-release layers or means
-
- 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
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/30—Imagewise removal using liquid means
- G03F7/3035—Imagewise removal using liquid means from printing plates fixed on a cylinder or on a curved surface; from printing cylinders
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C1/00—Forme preparation
- B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
- B41C1/1008—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials
- B41C1/1016—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials characterised by structural details, e.g. protective layers, backcoat layers or several imaging layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C2201/00—Location, type or constituents of the non-imaging layers in lithographic printing formes
- B41C2201/02—Cover layers; Protective layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C2201/00—Location, type or constituents of the non-imaging layers in lithographic printing formes
- B41C2201/10—Location, type or constituents of the non-imaging layers in lithographic printing formes characterised by inorganic compounds, e.g. pigments
-
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
- B41C2210/22—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by organic non-macromolecular additives, e.g. dyes, UV-absorbers, plasticisers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
- B41C2210/24—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by a macromolecular compound or binder obtained by reactions involving carbon-to-carbon unsaturated bonds, e.g. acrylics, vinyl polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
- B41C2210/26—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by a macromolecular compound or binder obtained by reactions not involving carbon-to-carbon unsaturated bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
- B41C2210/26—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by a macromolecular compound or binder obtained by reactions not involving carbon-to-carbon unsaturated bonds
- B41C2210/266—Polyurethanes; Polyureas
Definitions
- the present invention relates to a lithographic printing plate precursor that can be directly made by laser image exposure.
- a lithographic printing plate comprises an oleophilic image area that receives ink during the printing process and a hydrophilic non-image area that receives dampening water.
- Lithographic printing utilizes the property that water and oil-based inks repel each other, so that the oleophilic image area of the lithographic printing plate is the ink receiving area, and the hydrophilic non-image area is dampened with the water receiving area (ink non-receiving area).
- a difference in ink adhesion is caused on the surface of the lithographic printing plate, and after ink is applied only to the image area, the ink is transferred to a printing medium such as paper and printed.
- a lithographic printing plate precursor in which an oleophilic photosensitive resin layer (image recording layer) is provided on a hydrophilic support is used.
- a mask such as a film
- development with an alkaline developer is performed to leave the image recording layer corresponding to the image area, and dissolve and remove the unnecessary image recording layer corresponding to the non-image area. And obtained a lithographic printing plate.
- lithographic printing plates are now available with CTP (computer to plate) technology. That is, a lithographic printing plate can be obtained by scanning and exposing a lithographic printing plate precursor directly using a laser or a laser diode without a lith film, and developing it.
- CTP computer to plate
- a method called “on-press development” is performed. That is, after the exposure of the lithographic printing plate precursor, conventional development is not performed, but it is mounted on a printing machine as it is, and unnecessary portions of the image recording layer are removed at the initial stage of a normal printing process.
- a method called “gum development” in which unnecessary portions of the image recording layer are removed with a finisher or gum solution having a pH close to neutral instead of a conventional highly alkaline developer is also performed. ing.
- a system using a lithographic printing plate precursor and a light source that can be handled in a bright room or under a yellow light is preferable from the viewpoint of ease of work.
- a solid-state laser such as a semiconductor laser or a YAG laser emitting an infrared ray of 1200 nm is used. Further, a UV laser can be used.
- Patent Documents 1 and 2 As a lithographic printing plate capable of on-press development, for example, in Patent Documents 1 and 2, a lithographic printing plate precursor having an image recording layer (thermosensitive layer) containing a microcapsule containing a polymerizable compound on a hydrophilic support. Is described. Patent Document 3 describes a lithographic printing plate precursor in which an image recording layer (photosensitive layer) containing an infrared absorber, a radical polymerization initiator, and a polymerizable compound is provided on a support.
- Patent Document 4 contains an actinic ray absorber, a polymerization initiator, and a polymerizable compound on a support, and has an image recording layer that can be removed by printing ink, dampening water, or both, Furthermore, a lithographic printing plate precursor having a protective layer (overcoat layer) containing an inorganic stratiform compound in this order is described. Thus, it is known that a lithographic printing plate precursor having high sensitivity and excellent on-press developability can be obtained by including an inorganic layered compound in a protective layer. However, since the inorganic stratiform compound is embedded in the image recording layer in the coating / drying stage and is difficult to remove, there is a problem that ink inking during printing and printing is lowered.
- Patent Document 5 on-press development is possible in which an image recording layer containing a polymerizable compound and a graft polymer having a polyethylene oxide chain in the side chain or a block polymer having a polyethylene oxide block is provided on a support.
- a planographic printing plate precursor is described.
- this planographic printing plate precursor is insufficient in both sensitivity and on-press developability.
- an on-press development type lithographic printing plate precursor capable of recording an image with a laser and maintaining sufficient sensitivity while having sufficient ink acceptability.
- a lithographic printing plate precursor having a support, an image recording layer, and a protective layer in this order, wherein the protective layer contains an inorganic stratiform compound, and the number of repeating units of alkylene oxide is 10 to 120.
- a lithographic printing plate precursor comprising a polymer compound having a moiety in an image recording layer. 2.
- 3. The lithographic printing plate precursor as described in 1 or 2 above, wherein the image recording layer contains an infrared absorber, a radical polymerization initiator and a radical polymerizable compound. 4). 4.
- y represents 10 to 120
- R 1 represents a hydrogen atom or an alkyl group
- R 2 represents a hydrogen atom or an organic group.
- R 3 to R 6 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or an aralkyl group.
- X ⁇ represents a counter anion.
- R 11 represents a hydrogen atom or a methyl group
- L 1 represents a linking group
- R 12 to R 14 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or an aralkyl group.
- X ⁇ represents a counter anion.
- the image recording layer is an image recording layer capable of forming an image after exposure by supplying at least one of printing ink and fountain solution on a printing machine to remove an unexposed portion.
- the content of the polymer compound having a poly (alkylene oxide) moiety having 10 to 120 repeating units of alkylene oxide is 10 to 90% by mass with respect to the total solid content in the image recording layer. 14.
- an on-press development type lithographic printing plate precursor capable of recording an image with a laser and maintaining sufficient sensitivity while having sufficient ink acceptability.
- the lithographic printing plate precursor according to the invention has an image recording layer on a support and a protective layer on the image recording layer.
- An undercoat layer may be provided between the support and the image recording layer.
- the lithographic printing plate precursor according to the invention has a protective layer (overcoat layer) on the image recording layer.
- the protective layer has a function of preventing scratches in the image recording layer and preventing ablation during high-illuminance laser exposure.
- Such an oxygen barrier protective layer is described in, for example, US Pat. No. 3,458,311 and Japanese Examined Patent Publication No. 55-49729.
- the low oxygen permeability polymer used for the protective layer either a water-soluble polymer or a water-insoluble polymer can be appropriately selected and used. Specific examples include polyvinyl alcohol, modified polyvinyl alcohol, polyvinyl pyrrolidone, water-soluble cellulose derivatives, poly (meth) acrylonitrile, and the like. More specifically, the polymers described in paragraph numbers [0172] to [0175] of JP-A-2008-195018 can be mentioned.
- the protective layer contains an inorganic layered compound.
- the inorganic stratiform compound can maintain high oxygen barrier properties even when the coating thickness of the protective layer is reduced, and thus contributes to achieving high sensitivity while reducing the on-press development load due to the protective layer.
- the protective layer of the present invention preferably contains an inorganic stratiform compound and uses the above low oxygen permeability polymer as a binder.
- the inorganic layered compound is a particle having a thin flat plate shape, for example, General formula A (B, C) 2-5 D 4 O 10 (OH, F, O) 2 [However, A is any of K, Na, and Ca, B and C are any of Fe (II), Fe (III), Mn, Al, Mg, and V, and D is Si or Al. And mica groups such as natural mica and synthetic mica, talc, teniolite, montmorillonite, saponite, hectorite, zirconium phosphate and the like represented by the formula 3MgO.4SiO.H 2 O.
- examples of natural mica include muscovite, soda mica, phlogopite, biotite and sericite.
- Synthetic mica includes non-swelling mica such as fluorine phlogopite mica 3 (AlSi 3 O 10 ) F 2 , potassium tetrasilicon mica KMg 2.5 (Si 4 O 10 ) F 2 , and Na tetrasilicic mica NaMg 2.5.
- mica is preferable, and fluorine-based swellable mica, which is a synthetic inorganic layered compound, is particularly useful. That is, this swellable synthetic mica and swellable clay minerals such as montmorillonite, saponite, hectorite, bentonite and the like have a laminated structure composed of unit crystal lattice layers with a thickness of about 10 to 15 mm, Atomic substitution is significantly greater than other clay minerals. As a result, the lattice layer is deficient in positive charges, and cations such as Na + , Ca 2+ and Mg 2+ are adsorbed between the layers in order to compensate for this.
- fluorine-based swellable mica which is a synthetic inorganic layered compound, is particularly useful. That is, this swellable synthetic mica and swellable clay minerals such as montmorillonite, saponite, hectorite, bentonite and the like have a laminated structure composed of unit crystal lattice layers with a thickness
- the cations present between these layers are called exchangeable cations and exchange with various cations.
- the cation between the layers is Li + or Na +
- the bond between the layered crystal lattices is weak because the ionic radius is small, and the layer swells greatly with water. If shear is applied in this state, it will be easily cleaved to form a stable sol in water.
- Bentonite and swellable synthetic mica have a strong tendency and are useful in the present invention, and swellable synthetic mica is particularly preferably used.
- the aspect ratio is preferably 20 or more, more preferably 100 or more, and particularly preferably 200 or more.
- the aspect ratio is the ratio of the major axis to the thickness of the particles, and can be measured from, for example, a projected view of the particles by a micrograph. The larger the aspect ratio, the greater the effect that can be obtained.
- the particle size of the inorganic stratiform compound used in the present invention is such that the average major axis is 0.3 to 20 ⁇ m, preferably 0.5 to 10 ⁇ m, particularly preferably 1 to 5 ⁇ m.
- the average thickness of the particles is 0.1 ⁇ m or less, preferably 0.05 ⁇ m or less, particularly preferably 0.01 ⁇ m or less.
- the swellable synthetic mica which is a representative compound among inorganic layered compounds, has a thickness of 1 to 50 nm and a surface size of about 1 to 20 ⁇ m.
- the coating film strength is improved, and the permeation of oxygen and moisture can be effectively prevented. Deterioration is prevented, and even when stored for a long time under high-humidity conditions, the storage stability of the planographic printing plate precursor does not deteriorate due to changes in humidity, and the storage stability is excellent.
- the content of the inorganic stratiform compound in the protective layer is preferably 5/1 to 1/100 by mass ratio with respect to the amount of binder used in the protective layer. Even when a plurality of types of inorganic layered compounds are used in combination, the total amount of these inorganic layered compounds is preferably the above-described mass ratio.
- the protective layer may 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, an ammonium salt or a phosphonium salt described in the explanation of the image recording layer described later can be contained in the protective layer.
- the protective layer is applied by a known method.
- the coating amount of the protective layer, the coating amount after drying is preferably in the range of 0.01 ⁇ 10g / m 2, more preferably in the range of 0.02 ⁇ 3g / m 2, and most preferably 0.
- the range is 02 to 1 g / m 2 .
- the image recording layer of the present invention is characterized by containing (A) a polymer compound having a poly (alkylene oxide) moiety having 10 to 120 repeating units of alkylene oxide.
- A a polymer compound having a poly (alkylene oxide) moiety having 10 to 120 repeating units of alkylene oxide.
- a polymer compound having a poly (alkylene oxide) moiety is referred to as a specific polymer compound.
- it is estimated as follows as a mechanism in which a specific high molecular compound improves inking property.
- the alkylene oxide long chain in the specific polymer compound interacts with the surface of the inorganic layered compound such as mica, and the specific polymer compound covers the surface of the inorganic layered compound, thereby reducing the hydrophilicity of the surface of the inorganic layered compound.
- the meat quality is improved.
- the image recording layer of the present invention preferably contains (B) an infrared absorber, (C) a radical polymerization initiator, and (D) a radical polymerizable compound.
- B an infrared absorber
- C a radical polymerization initiator
- D a radical polymerizable compound
- the specific polymer compound in which the number of repeating units of alkylene oxide used in the lithographic printing plate precursor according to the invention is 10 to 120 is poly (alkylene).
- Oxide) moiety may be present in the main chain or in the side chain, and even in a graft polymer having poly (alkylene oxide) in the side chain, the poly (alkylene oxide) -containing block and (alkylene oxide) non- It may be a block copolymer with a block composed of contained repeating units. When it has in a principal chain, a polyurethane resin is preferable.
- the main chain polymer in the case of the side chain includes acrylic resin, polyvinyl acetal resin, polyurethane resin, polyurea resin, polyimide resin, polyamide resin, epoxy resin, methacrylic resin, polystyrene resin, novolac type phenol resin, polyester resin Synthetic rubber and natural rubber can be mentioned, and acrylic resin is particularly preferable.
- This specific polymer compound is substantially free of perfluoroalkyl groups.
- “Substantially free of perfluoroalkyl group” means that the mass ratio of fluorine atoms present as a perfluoroalkyl group in the specific 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 one in which all hydrogen atoms of the alkyl group are substituted with fluorine atoms.
- the alkylene oxide is preferably an alkylene oxide having 2 to 6 carbon atoms, particularly ethylene oxide or propylene oxide.
- the number of repeating alkylene oxides at the poly (alkylene oxide) site is 10 to 120, preferably 20 to 70, and more preferably 20 to 50. If the number of repeating alkylene oxides is less than 10, ink acceptability cannot be improved. On the other hand, if the number of repetitions exceeds 120, both the printing durability due to wear and the printing durability due to ink acceptability are deteriorated.
- the poly (alkylene oxide) moiety is preferably contained in the structure represented by the general formula (1) as a side chain of the specific polymer compound. More preferably, it is contained in the structure represented by the general formula (1) as a side chain of the acrylic resin.
- y represents 10 to 120, preferably 20 to 70, and more preferably 20 to 50.
- 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 thereof include a pentyl group, an isopentyl group, a neopentyl group, an n-hexyl group, an isohexyl group, a 1,1-dimethylbutyl group, a 2,2-dimethylbutyl group, a cyclopentyl group, and a cyclohexyl group.
- R 1 is preferably a hydrogen atom or a methyl
- 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 having an ethylenically unsaturated bond in the main chain of the molecule include poly-1,4-butadiene and poly-1,4-isoprene.
- polymers having ethylenically unsaturated bonds in the side chain of the molecule are polymers of esters or amides of acrylic acid or methacrylic acid, where the ester or amide residue (R of —COOR or —CONHR) is Mention may be made of polymers having an ethylenically unsaturated bond.
- 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.
- the specific polymer compound having crosslinkability is, for example, a free radical (polymerization initiation radical or a growth radical in the polymerization process of the polymerizable compound) is added to the crosslinkable functional group, and polymerization of the polymerizable compound is performed directly between the polymers. Addition polymerization through a chain forms a cross-link between polymer molecules and cures. Alternatively, atoms in the polymer (eg, hydrogen atoms on carbon atoms adjacent to the functional bridging group) are abstracted by free radicals to form polymer radicals that are bonded together, thereby causing cross-linking between polymer molecules. Forms and cures.
- a free radical polymerization initiation radical or a growth radical in the polymerization process of the polymerizable compound
- 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, most preferably 2.0 to 5.5 mmol. Within this range, good sensitivity and good storage stability can be obtained.
- the specific polymer compound of the present invention may further contain a copolymer component for the purpose of improving various performances such as image strength as long as the effects of the present invention are not impaired.
- a copolymer component for the purpose of improving various performances such as image strength as long as the effects of the present invention are not impaired.
- a structure of a preferable copolymerization component what is represented by the following general formula (4) 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 (4) 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.
- acrylic esters such as alkyl acrylate (the alkyl group preferably has 1 to 20 carbon atoms), such as methyl acrylate, ethyl acrylate, propyl acrylate, acrylic acid Butyl, amyl acrylate, ethyl hexyl acrylate, octyl acrylate, 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, glycidyl acrylate, benzyl acrylate, etc.), aryl acrylate (For example, phenyl acrylate), alkyl methacrylate (the alkyl group preferably has 1 to 20 carbon atoms) and other methacrylic acid esters (for example, methyl methacrylate) Rate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate,
- methylstyrene for example, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene
- Chloromethylstyrene Ethoxymethyl styrene and acetoxymethyl styrene acrylonitrile
- methacrylonitrile a radical polymerizable compound containing a carboxylic acid (acrylic acid, methacrylic acid, and salts of these acids group).
- Acrylonitrile is preferred from the viewpoint of printing durability.
- the ratio of the repeating unit having the 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%.
- the polymer compound in the present invention 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.
- Mw mass average molar mass
- hydrophilic polymer compounds such as polyacrylic acid and polyvinyl alcohol described in JP-A-2008-195018 can be used in combination. Further, a lipophilic polymer compound and a hydrophilic polymer compound can be used in combination.
- the form of the specific polymer compound of the present invention may be present in the image recording layer as a binder that functions as a connecting material for each material, or may be present in the form of fine particles.
- the average particle diameter is generally in the range of 10 to 1000 nm, preferably in the range of 20 to 300 nm, and particularly preferably in the range of 30 to 120 nm.
- the content of the specific polymer compound of the present invention is not particularly limited, but is generally 10 to 90% by mass, preferably 10 to 80% by mass, based on the total solid content of the image recording layer. Particularly preferred is 15 to 70% by mass.
- the infrared absorber has a function of converting absorbed infrared light into heat and a function of exciting with infrared light to transfer electrons and / or energy to a radical polymerization initiator described later.
- the infrared absorber used in the present invention is a dye or pigment having an absorption maximum at a wavelength of 760 to 1200 nm.
- infrared absorber compounds described in paragraph numbers [0058] to [0087] of JP-A-2008-195018 can be used.
- preferable infrared absorbers include cyanine dyes, squarylium dyes, pyrylium salts, and nickel thiolate complexes.
- 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 aromatic hydrocarbon group having 6 to 10 carbon atoms, or an alkyl group having 1 to 8 carbon atoms.
- X 2 represents an oxygen atom or a sulfur atom
- L 1 represents a hydrocarbon group having 1 to 12 carbon atoms, an aromatic ring having a hetero atom, 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. From the storage stability of the image recording layer coating solution, R 1 and R 2 are preferably hydrocarbon groups having 2 or more carbon atoms, and R 1 and R 2 are bonded to each other to form a 5-membered ring. Alternatively, it is particularly preferable that a 6-membered ring is formed.
- Ar 1 and Ar 2 may be the same or different and each represents an aromatic hydrocarbon group which may have a substituent.
- Preferred aromatic hydrocarbon 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 charge neutralization 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.
- Specific examples of the cyanine dye represented by the general formula (a) that can be preferably used in the present invention include paragraph numbers [0017] to [0019] of JP-A No. 2001-133969 and JP-A No. 2002-023360. Examples thereof include those described in paragraph Nos. [0012] to [0021] of Japanese Patent Laid-Open No. 2002-04638 and paragraph Nos. [0012] to [0037] of JP-A No. 2002-040638. These infrared absorbers may be used alone or in combination of two or more.
- pigment compounds described in JP 2008-195018 A [0072] to [0076] are preferable. It can also be used in combination with the above dyes.
- the content of the infrared absorber in the image recording layer in the present invention is preferably 0.1 to 10.0% by mass, more preferably 0.5 to 5.0% by mass based on the total solid content of the image recording layer. .
- the radical polymerization initiator used for this invention is a compound which generate
- the generated radical polymerizes and cures the radical polymerizable compound.
- onium salts are preferable, and iodonium salts, sulfonium salts, and azinium salts are most preferable. Specific examples of these compounds are shown below, but are not limited thereto.
- the radical 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 constituting the image recording layer. Can be added.
- the radical polymerizable compound that can be used in the present invention is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and has at least one terminal ethylenically unsaturated bond, Preferably it is selected from compounds having two or more.
- Such a compound group is widely known in the industrial field, and can be used without any particular limitation in the present invention. These have chemical forms such as monomers, prepolymers, i.e. dimers, trimers and oligomers, or mixtures thereof and their (co) polymers.
- esters of aliphatic polyhydric alcohol compounds and unsaturated carboxylic acids for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid and the like.
- Another preferred radically polymerizable compound includes a polymerizable compound having an isocyanuric acid structure described in JP-A-2005-329708.
- 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 radical polymerizable compound is preferably used in the range of 5 to 80% by mass, more preferably 25 to 75% by mass, based on the total solid content of the image recording layer.
- (E) Ammonium salt or phosphonium salt The addition of a specific polymer compound having 10 to 120 repeating units of alkylene oxide can improve the ink inking property of the lithographic printing plate precursor of the present invention. By using at least one selected from salts in combination, the inking property is further improved. Among these, it is preferable to use an ammonium salt.
- these compounds function as a surface coating agent for the inorganic layered compound and prevent a decrease in ink depositability.
- ammonium salt those represented by the following general formula (2) are preferable.
- R 3 to R 6 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or an aralkyl group. Of these, an aryl group and an aralkyl group are preferable.
- alkyl group represented by R 3 to R 6 examples include linear, branched or cyclic alkyl groups having 1 to 18 carbon atoms. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, cyclobutyl group, n-amyl group, isoamyl group -Group, sec-amyl group, t-amyl group, neopentyl group, cyclopentyl group, n-hexyl group, isohexyl group, sec-hexyl group, t-hexyl group, cyclohexyl group, cyclohexylmethyl group, cyclopentyl group, cyclopropylmethyl Group, cyclohexylmethyl group, cyclobutylmethyl group, linear or branche
- Examples of the aralkyl group represented by R 3 to R 6 include benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, and 3-naphthylpropyl group. Groups are preferred.
- the aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms, and examples thereof include phenyl, p-methylphenyl, and naphthyl.
- R 3 to R 6 may have a substituent.
- a trifluoromethyl group, a fluoro group, a chloro group, a bromo group, a methoxy group, a hydroxy group, a nitro group, a vinyl group, a dimethylamino group, a phenyl group, a methoxycarbonyl group, and an ethoxycarbonyl group are preferable.
- Fluoro group, chloro group, bromo group, methoxy group, hydroxy group, vinyl group, phenyl group, methoxycarbonyl group, and ethoxycarbonyl group are more preferable. These groups may be further substituted with the same substituent.
- R 3 to R 6 may all be the same or all different, or two of the three may be the same and can be arbitrarily selected.
- X ⁇ represents a counter anion.
- the counter anion may be an organic anion or an inorganic anion.
- X ⁇ includes F ⁇ , Cl ⁇ , Br ⁇ , I ⁇ , an optionally substituted benzene sulfonate anion, a methyl sulfate anion, an ethyl sulfate anion, a propyl sulfate anion, and a butyl sulfate anion which may be branched.
- amyl sulfate anion which may be branched, PF 6 ⁇ , BF 4 ⁇ and B (C 6 F 5 ) 4 — .
- Cl ⁇ , Br ⁇ , benzenesulfonate anion, toluenesulfonate anion, methyl sulfate anion, ethyl sulfate anion, propyl sulfate anion, PF 6 ⁇ , BF 4 ⁇ and B (C 6 F 5 ) 4 ⁇ are preferable.
- ammonium salts include imidazolinium salts, benzimidazolinium salts, pyridinium salts, and quinolinium salts.
- ammonium salts include polymers containing ammonium groups.
- a polymer having a repeating unit represented by the following general formula (3) is preferable.
- R 11 represents a hydrogen atom or a methyl group.
- R 12 to R 14 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or an aralkyl group. Of these, an aryl group and an aralkyl group are preferable.
- alkyl group represented by R 12 to R 14 examples include linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, cyclobutyl group, n-amyl group, isoamyl group -Group, sec-amyl group, t-amyl group, neopentyl group, cyclopentyl group, n-hexyl group, isohexyl group, sec-hexyl group, t-hexyl group, cyclohexyl group, cyclohexylmethyl group, cyclopentyl group, cyclopropylmethyl A group, a cyclohexylmethyl group, a cyclobutylmethyl group
- R 12 to R 14 may be all the same, all different, or two of the three may be the same.
- the aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms, and examples thereof include phenyl, p-methylphenyl, and naphthyl.
- L 1 represents a linking group.
- the linking group include a linking group having at least one selected from a phenylene group, a carbonyloxy group, and a carbonylimino group.
- a linking group having a carbonyloxy group is preferable, and specific examples include —COO (CH 2 ) n —.
- n represents an integer of 1 to 4, and 2 or 3 is more preferable.
- X ⁇ represents a counter anion.
- an organic anion may be an inorganic anion, but an aryl group, an aralkyl group, an organic sulfonate anion having a substituent carbon atoms selected from 6 or more alkyl groups, borate anion and PF 6 - are preferred, Organic borate anions and PF 6 - are preferred.
- the organic borate anion an organic borate anion having a structure represented by the following general formula (5) is more preferable.
- the counter anion is an organic borate anion, the curing of the image portion further proceeds with the increase in sensitivity, and the water penetration is suppressed, so that the ink can be further improved in the printing durability. Become good.
- R 1 to R 4 each independently represents a monovalent organic group.
- the monovalent organic group represented by R 1 to R 4 include an alkyl group, an alkenyl group, an aryl group, an alkynyl group, and a cycloalkyl group. Among them, an aryl group is preferable.
- These organic groups may have a substituent. Examples of the substituent that can be introduced include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a halogen atom, an alkoxy group, an alkoxycarbonyl group, an amino group, and a cyano group.
- R 1 to R 4 are preferably aryl groups having an electron-withdrawing group as a substituent.
- a halogen atom and a fluoroalkyl group are preferable, and a fluorine atom and a trifluoromethyl group are particularly preferable.
- the polymer having the repeating unit represented by the general formula (3) can have other copolymerization components.
- Other copolymer components are not particularly limited as long as they can be copolymerized, but (meth) acrylates are preferred.
- the R of (CO) OR side chain of (meth) acrylate is an alkyl group having 1 to 21 carbon atoms, an aralkyl group, an aryl group, — (C 2 H 4 O) n —R 5 , or — (C 3 H 6 O). ) n -R 5, and the like.
- R 5 represents a hydrogen atom, a methyl group or an ethyl group.
- n represents an integer of 1 to 3.
- the content of the repeating unit represented by the general formula (3) in the polymer compound is preferably in the range of 5 to 80 mol%.
- the ammonium salt-containing polymer preferably has a reduced specific viscosity (unit: cSt / g / ml) determined by the following measurement method, preferably in the range of 5 to 120, more preferably in the range of 10 to 110. A range of 15 to 100 is particularly preferable.
- the content of the ammonium salt or phosphonium salt is preferably 0.01 to 30.0% by mass, more preferably 0.1 to 15.0% by mass, and 1 to 5% by mass with respect to the total solid content of the image recording layer. % Is more preferable.
- a hydrophobized precursor can be used to improve on-press developability.
- the hydrophobized precursor in the present invention means fine particles capable of converting the image recording layer to hydrophobic when heat is applied.
- the fine particles are preferably at least one particle selected from hydrophobic thermoplastic polymer fine particles, heat-reactive polymer fine particles, microcapsules enclosing a hydrophobic compound, and microgel (crosslinked polymer fine particles).
- polymer fine particles and microgels having a polymerizable group are preferable.
- Hydrophobic thermoplastic polymer fine particles include Research Disclosure No. 1 of January 1992. 331,003, JP-A-9-123387, JP-A-9-131850, JP-A-9-171249, JP-A-9-171250, and European Patent No. 931647 are suitable.
- Polymers constituting such polymer fine particles include ethylene, styrene, vinyl chloride, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, vinylidene chloride, acrylonitrile, vinyl carbazole, and polyalkylene structures. Mention may be made of homopolymers or copolymers of monomers such as acrylates or methacrylates or mixtures thereof. Among them, more preferred are polystyrene and polymethyl methacrylate.
- the average particle diameter of the hydrophobic thermoplastic polymer fine particles used in the present invention is preferably 0.01 to 2.0 ⁇ m.
- heat-reactive polymer fine particles used in the present invention include polymer fine particles having a heat-reactive group, and these form a hydrophobic region by cross-linking due to a heat reaction and a functional group change at that time.
- the thermally reactive group in the polymer fine particle having a thermally reactive group used in the present invention may be any functional group that performs a reaction as long as a chemical bond is formed, but is an ethylenically unsaturated group that performs a radical polymerization reaction.
- a functional group having an active hydrogen atom as a reaction partner for example, an amino group, a hydroxy group, a carboxy group, etc.
- a carboxy group for performing a condensation reaction for example, a hydroxy group or an amino group as a reaction partner, a ring-opening addition reaction
- suitable acid anhydrides and amino or hydroxy groups that are reaction partners That.
- the microcapsules used in the present invention for example, as described in JP-A Nos. 2001-277740 and 2001-277742, all or part of the constituent components of the image recording layer are encapsulated in the microcapsules. Is.
- the constituent components of the image recording layer can also be contained outside the microcapsules.
- the image recording layer containing the microcapsule includes a hydrophobic constituent component in the microcapsule and a hydrophilic constituent component outside the microcapsule.
- a cross-linked resin particle that is, an embodiment containing microgel may be used.
- This microgel can contain a part of the constituents of the image recording layer in and / or on the surface thereof, and in particular, an embodiment in which a reactive microgel is formed by having a radically polymerizable compound on the surface of the microgel. It is particularly preferable from the viewpoint of formation sensitivity and printing durability.
- the average particle size of the above microcapsules and microgels is preferably 0.01 to 3.0 ⁇ m. 0.05 to 2.0 ⁇ m is more preferable, and 0.10 to 1.0 ⁇ m is particularly preferable. Within this range, good resolution and stability over time can be obtained.
- the content of the hydrophobizing precursor is preferably in the range of 5 to 90% by mass as the solid content concentration of the image recording layer.
- the image recording layer in the invention 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, Polyhydroxys such as pentaerythritol and tris (2-hydroxyethyl) isocyanurate, organic amines such as triethanolamine and diethanolamine 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
- organic sulfonates include alkyl sulfonates such as sodium n-butyl sulfonate, sodium n-hexyl sulfonate, sodium 2-ethylhexyl sulfonate, sodium cyclohexyl sulfonate, and sodium n-octyl sulfonate.
- organic sulfate examples include polyethylene oxide alkyl, alkenyl, alkynyl, aryl or heterocyclic monoether sulfates.
- the ethylene oxide unit is preferably 1 to 4, and the salt is preferably a sodium salt, potassium salt or lithium salt.
- 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 above low molecular weight hydrophilic compound has a small hydrophobic part structure and almost no surface-active action, so that dampening water penetrates into the exposed part of the image recording layer (image part) and the hydrophobicity and film strength of the image part. Ink acceptability and printing durability of the image recording layer can be maintained satisfactorily.
- the amount of these low molecular weight hydrophilic compounds added to the image recording layer is preferably 0.5% by mass or more and 20% by mass or less of the total solid content of the image recording layer. More preferably, it is 1 mass% or more and 10 mass% or less, More preferably, it is 2 mass% or more and 8 mass% or less. In this range, good on-press developability and printing durability can be obtained. These compounds may be used alone or in combination of two or more.
- a surfactant in the image recording layer of the present invention, can be used in order to promote on-press developability and improve the coated surface state.
- the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, and fluorosurfactants.
- Surfactant may be used independently and may be used in combination of 2 or more type.
- halide ions are contained as impurities or counter ions in the surfactant, it is preferable to remove or exchange with other anions by a method such as desalting or ion exchange.
- the nonionic surfactant used in the present invention is not particularly limited, and conventionally known nonionic surfactants can be used.
- nonionic surfactants can be used.
- polyoxyethylene alkyl ethers polyoxyethylene alkyl phenyl ethers, polyoxyethylene polystyryl phenyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, glycerin fatty acid partial esters, sorbitan fatty acid partial esters, pentaerythritol Fatty acid partial esters, propylene glycol mono fatty acid esters, sucrose fatty acid partial esters, polyoxyethylene sorbitan fatty acid partial esters, polyoxyethylene sorbitol fatty acid partial esters, polyethylene glycol fatty acid esters, polyglycerin fatty acid partial esters, Polyoxyethylenated castor oil, polyoxyethylene glycerin fatty acid partial esters, fatty acid diethanolamides, N N- bis-2-hydroxyalky
- the anionic surfactant used in the present invention is not particularly limited, and conventionally known anionic surfactants can be used.
- anionic surfactants can be used.
- the cationic surfactant used in the present invention is not particularly limited, and conventionally known cationic surfactants can be used. Examples thereof include alkylamine salts, quaternary ammonium salts, polyoxyethylene alkylamine salts, and polyethylene polyamine derivatives.
- As the counter anion of the cationic surfactant it is preferable to select one other than halide ions (sulfate ion, hydrogen sulfate ion, hydroxide ion, phosphate ion, alkyl sulfonate ion, aryl sulfonate ion, etc.). .
- amphoteric surfactant used in the present invention is not particularly limited, and conventionally known amphoteric surfactants can be used. Examples thereof include carboxybetaines, aminocarboxylic acids, sulfobetaines, aminosulfuric esters, and imidazolines.
- polyoxyethylene can be read as “polyoxyalkylene” such as polyoxymethylene, polyoxypropylene, polyoxybutylene, etc. These surfactants can also be used.
- More preferable surfactants include fluorine-based surfactants containing a perfluoroalkyl group in the molecule.
- fluorosurfactants include ionic types such as perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, and perfluoroalkyl phosphates; amphoteric types such as perfluoroalkyl betaines; Cation type such as trimethylammonium salt; perfluoroalkylamine oxide, perfluoroalkylethylene oxide adduct, oligomer containing perfluoroalkyl group and hydrophilic group, oligomer containing perfluoroalkyl group and lipophilic group, perfluoroalkyl Nonionic types such as an oligomer containing a group, a hydrophilic group and a lipophilic group, and a urethane containing a perfluoroalkyl group and a lipophilic group.
- fluorine-based surfactants described in JP-A Nos. 62-170950, 62-226143, and 60-168144 for example, acrylates or methacrylates containing perfluoroalkyl groups, and poly ( Oxyalkylene) acrylate or methacrylate copolymers, polyoxypropylene / polyoxyethylene / block copolymer end-perfluoroalkyl etherified products, and the like are also preferred.
- Surfactant can be used individually or in combination of 2 or more types.
- the content of the surfactant is preferably from 0.01 to 10% by mass, more preferably from 0.1 to 5% by mass, based on the total solid content of the image recording layer.
- the content is 0.01% by mass or more, the surface activity is sufficiently exhibited and the uniformity of the coated surface is obtained.
- the content is 10% by mass or less, when one layer, for example, a protective layer, is applied on the image recording layer, no repelling occurs and good performance is obtained.
- the image recording layer according to the present invention is prepared by mixing the necessary components described above with known solvents as described in paragraph numbers [0142] to [0143] of JP-A-2008-195018, for example.
- a coating solution is prepared by dispersing or dissolving in a coating solution, which is formed by applying the coating solution on a support by a known method such as bar coater coating and drying.
- the image recording layer coating amount (solid content) on the support obtained after coating and drying varies depending on the application, but is generally preferably 0.3 to 3.0 g / m 2 . Within this range, good sensitivity and good film properties of the image recording layer can be obtained.
- an undercoat layer (sometimes referred to as an intermediate layer) is preferably provided between the image recording layer and the support.
- the undercoat layer enhances the adhesion between the support and the image recording layer in the exposed area, and easily peels off the image recording layer from the support in the unexposed area. Contributes to improvement.
- the undercoat layer functions as a heat insulating layer, thereby preventing the heat generated by the exposure from diffusing to the support and reducing 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. More preferable are polymer resins having an adsorptive group, a hydrophilic group, and a crosslinkable group that can be adsorbed on the support surface, as described in JP-A Nos. 2005-125749 and 2006-188038. It is done.
- the polymer resin 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 adsorptive 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.
- an adsorptive 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.
- Examples thereof include a polymer resin that is a copolymer of a monomer, a monomer having a hydrophilic sulfo group, and a monomer having a polymerizable crosslinkable group such as a methacryl group or an allyl group.
- This polymer resin may have a crosslinkable group introduced by salt formation between a polar substituent of the polymer resin, a substituent having a counter charge and a compound having an ethylenically unsaturated bond,
- Other monomers, preferably hydrophilic monomers may be further copolymerized.
- the content of unsaturated double bonds in the polymer resin for the undercoat layer is preferably 0.1 to 10.0 mmol, and most preferably 2.0 to 5.5 mmol per 1 g of the polymer resin.
- the polymer resin 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 of the present invention comprises, in addition to the above undercoat compound, a chelating agent, a secondary or tertiary amine, a polymerization inhibitor, an amino group, or a functional group having a polymerization inhibiting ability, in order to prevent contamination over time.
- a chelating agent 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 to 100 mg / m 2 , and more preferably 1 to 30 mg / m 2 .
- a known support As the support used in the lithographic printing plate precursor according to the invention, a known support is used. Of these, an aluminum plate that has been roughened and anodized by a known method is preferred. In addition, the aluminum plate is subjected to micropore enlargement treatment or sealing treatment of an anodized film described in JP-A-2001-253181 or JP-A-2001-322365, and US Pat. 714,066, 3,181,461, 3,280,734 and 3,902,734, or alkali metal silicates as described in U.S. Pat. Surface hydrophilization treatment with polyvinylphosphonic acid or the like as described in each specification of 3,276,868, 4,153,461 and 4,689,272 is appropriately performed and performed. be able to.
- the support preferably has a center line average roughness of 0.10 to 1.2 ⁇ m.
- the support of the present invention includes an organic polymer compound described in JP-A-5-45885 and a silicon alkoxy compound described in JP-A-6-35174 on the back surface.
- a backcoat layer can be provided.
- the plate making of the lithographic printing plate precursor according to the invention is preferably carried out by an on-press development method.
- the on-press development method includes an image exposure process for a lithographic printing plate precursor, a printing process in which an oil-based ink and an aqueous component are supplied and printed without performing any development process on the exposed lithographic printing plate precursor. And the unexposed portion of the lithographic printing plate precursor is removed during the printing process.
- Imagewise exposure may be performed on the printing machine after the lithographic printing plate precursor is mounted on the printing machine, or may be separately performed with a plate setter or the like. In the latter case, the exposed lithographic printing plate precursor is mounted on a printing machine without undergoing a development process.
- an on-press development process that is, an image recording layer in an unexposed area is removed at an early stage of printing, Accordingly, the surface of the hydrophilic support is exposed to form a non-image part.
- an oil-based ink and the aqueous component ordinary lithographic printing ink and fountain solution are used. This will be described in more detail below.
- the light source used for image exposure is preferably a laser.
- the laser used in the present invention is not particularly limited, and preferred examples include solid lasers and semiconductor lasers that irradiate infrared rays having a wavelength of 760 to 1200 nm.
- 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 exposed lithographic printing plate precursor is mounted on the plate cylinder of a printing press.
- image exposure is performed after a lithographic printing plate precursor is mounted on a plate cylinder of the printing press.
- the image recording layer cured by exposure has a printing ink acceptance having an oleophilic surface in the exposed portion of the image recording layer. Forming part.
- 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.
- dampening water or printing ink may be supplied to the printing plate first, but printing is first performed in order to prevent the dampening water from being contaminated by the removed image recording layer components. It is preferable to supply ink.
- the lithographic printing plate precursor according to the invention is developed on the machine on an offset printing machine and used as it is for printing a large number of sheets.
- This plate was etched by being immersed in a 25 mass% sodium hydroxide aqueous solution at 45 ° C for 9 seconds, washed with water, further immersed in 20 mass% nitric acid at 60 ° C for 20 seconds, and washed with water. At this time, the etching amount of the grained surface was about 3 g / m 2 .
- an electrochemical roughening treatment was performed continuously using an alternating voltage of 60 Hz.
- the electrolytic solution at this time was a 1% by mass nitric acid aqueous solution (containing 0.5% by mass of aluminum ions) and a liquid temperature of 50 ° C.
- the AC power source waveform is electrochemical roughening treatment using a trapezoidal rectangular wave alternating current with a time ratio TP of 0.8 msec until the current value reaches a peak from zero, a duty ratio of 1: 1, and a trapezoidal rectangular wave alternating current. Went. Ferrite was used for the auxiliary anode.
- the current density was 30 A / dm 2 at the peak current value, and 5% of the current flowing from the power source was shunted to the auxiliary anode.
- the amount of electricity in nitric acid electrolysis was 175 C / dm 2 when the aluminum plate was the anode. Then, water washing by spraying was performed.
- nitric acid electrolysis was performed with an aqueous solution of 0.5% by mass of hydrochloric acid (containing 0.5% by mass of aluminum ions) and an electrolytic solution having a liquid temperature of 50 ° C. under the condition of an electric quantity of 50 C / dm 2 when the aluminum plate was the anode.
- Electrochemical surface roughening treatment was carried out in the same manner as above, followed by washing with water by spraying.
- the plate was provided with a direct current anodic oxide film having a current density of 15 A / dm 2 and a current density of 15 g / m 2 using 15% by mass sulfuric acid (containing 0.5% by mass of aluminum ions) as an electrolytic solution, followed by washing with water.
- the support body (1) It dried and produced the support body (1). Thereafter, in order to ensure the hydrophilicity of the non-image area, the support (1) was subjected to a silicate treatment at 60 ° C. for 10 seconds using an aqueous 2.5 mass% No. 3 sodium silicate solution, and then washed with water for support. Body (2) was obtained. The adhesion amount of Si was 10 mg / m 2 . The centerline average roughness (Ra) of this substrate was measured using a needle having a diameter of 2 ⁇ m and found to be 0.51 ⁇ m.
- undercoat layer coating solution (1) is applied onto the support (2) so that the dry coating amount is 20 mg / m 2 , and used in the following experiments.
- a support having a layer was prepared.
- the image recording layer coating solution (1) having the following composition was bar-coated on the undercoat layer formed as described above, and then oven-dried at 100 ° C for 60 seconds to obtain a dry coating amount. An image recording layer of 1.0 g / m 2 was formed.
- the image recording layer coating solution (1) was obtained by mixing and stirring the following photosensitive solution (1) and microgel solution (1) immediately before coating.
- the structure of the polymerization initiator (1), infrared absorbing dye (1), low molecular weight hydrophilic compound (1), and fluorosurfactant (1) and the method for synthesizing the microgel (1) are shown below. Street.
- microgel (1) As an oil phase component, trimethylolpropane and xylene diisocyanate adduct (Mitsui Chemical Polyurethane Co., Ltd., Takenate D-110N) 10 g, pentaerythritol triacrylate (Nippon Kayaku Co., Ltd., SR444) 3.15 g, And 0.1 g of Pionein A-41C (manufactured by Takemoto Yushi Co., Ltd.) was dissolved in 17 g of ethyl acetate. As an aqueous phase component, 40 g of a 4% by mass aqueous solution of PVA-205 was prepared.
- the oil phase component and the water phase component were mixed and emulsified for 10 minutes at 12,000 rpm using a homogenizer.
- the obtained emulsion was added to 25 g of distilled water, 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, and this was used as the microgel (1).
- the average particle size of the microgel was measured by the light scattering method, the average particle size was 0.2 ⁇ m.
- the structure of the comparative polymer compound used in the comparative example is as follows.
- the obtained lithographic printing plate precursor was subjected to Fujifilm's Luxel PLASETTERT-6000III equipped with an infrared semiconductor laser under the conditions of external drum rotation speed 1000 rpm, laser output 70%, resolution 2400 dpi. Exposed.
- the exposure image included a solid image and a 50% halftone dot chart of a 20 ⁇ m dot FM screen.
- the obtained exposed original plate was attached to a plate cylinder of a printing machine LITHRONE 26 manufactured by Komori Corporation without developing.
- 100 sheets were printed on Tokuhishi Art (76.5 kg) paper at a printing speed of 10,000 sheets per hour.
- the removal of the unexposed portion of the image recording layer on the printing machine was completed, and the number of printing sheets required until ink was not transferred to the non-image portion was measured as on-press developability. The results are shown in Table 1.
- the above protective layer coating solution (1) was further bar coated on the image recording layer and then oven-dried at 120 ° C. for 60 seconds to obtain a dry coating amount of 0.15 g / m 2 .
- a protective layer was formed to obtain lithographic printing plate precursors (21) to (29) [for Examples 13 to 21] and (45) to (46) [for Comparative Examples 5 to 6].
- the lithographic printing plate precursor (47) [for Comparative Example 7] was the same as the lithographic printing plate precursor (13) except that the protective layer coating solution (2) was used instead of the protective layer coating solution (1). Made.
- lithographic printing plate precursor (30) Preparation of lithographic printing plate precursor (30)]
- the lithographic printing plate precursor (21) was used except that the image recording layer coating liquid (5) using the following polymer fine particle aqueous dispersion (1) was used instead of the specific polymer compound of the image recording layer coating liquid (4).
- a lithographic printing plate precursor (30) [for Example 22] was obtained in the same manner as in the preparation.
- the addition amount of the polymer fine particle aqueous dispersion is 19.0 g in the image recording layer coating liquid (5).
- the particle size distribution of the polymer fine particles had a maximum value at a particle size of 150 nm.
- the particle size distribution is obtained by taking an electron micrograph of polymer fine particles, measuring a total of 5000 fine particle sizes on the photograph, and a logarithmic scale between 0 and the maximum value of the obtained particle size measurement values. 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.
- Lithographic printing is performed in the same manner as in the production of the lithographic printing plate precursor (21) except that the image recording layer coating solution (6) obtained by adding 0.3 g of the following compound (c1) to the image recording coating solution (5) is used.
- a plate precursor (31) [for Example 23] was obtained.
- Lithographic printing is performed in the same manner as in the production of the lithographic printing plate precursor (21) except that the image recording layer coating solution (7) obtained by adding 0.3 g of the following compound (d1) to the image recording coating solution (5) is used.
- a plate precursor (32) [for Example 24] was obtained.
- ammonium salts (a1), (a2), (b1), and (b2) in Table 1 are as follows.
- Comparative Example 4 and Comparative Example 7 using a protective layer containing no inorganic stratiform compound have low printing durability due to insufficient oxygen barrier properties and low sensitivity.
- Comparative Examples 1, 2 and 5 using a protective layer containing an inorganic stratiform compound maintain high sensitivity and good printing durability due to wear, but are polymers having a smaller number of alkylene oxide repeating units than the scope of the present invention. Ink acceptability is low due to the use of compounds.
- Comparative Examples 3 and 6 using a polymer compound having a larger number of alkylene oxide repeating units than the range of the present invention the printing durability due to wear decreases.
- the examples using the present invention can achieve both on-press developability, printing durability due to abrasion, and ink acceptability while maintaining high sensitivity.
- onium salts (c1) and (d1) in Table 3 are as follows.
- the lithographic printing plate precursor according to the present invention is capable of image recording by laser and on-press development, has high ink acceptability while maintaining high sensitivity, and is suitably used in various printing fields.
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Architecture (AREA)
- Structural Engineering (AREA)
- Optics & Photonics (AREA)
- Thermal Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials For Photolithography (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Printing Plates And Materials Therefor (AREA)
Abstract
Description
この平版印刷版を作製するため、従来は、親水性の支持体上に親油性の感光性樹脂層(画像記録層)を設けてなる平版印刷版原版(PS版)を用い、PS版にリスフィルムなどのマスクを通した露光を行った後、アルカリ性現像液などによる現像処理を行い、画像部に対応する画像記録層を残存させ、非画像部に対応する不要な画像記録層を溶解除去して、平版印刷版を得ていた。
また、簡易現像の方法としては、画像記録層の不要部分の除去を、従来の高アルカリ性現像液ではなく、pHが中性に近いフィニッシャー又はガム液によって行う「ガム現像」と呼ばれる方法も行われている。
しかしながら、無機質の層状化合物が塗布・乾燥段階で画像記録層中に潜りこみ、除去しづらくなるため、刷り出し及び印刷途中でのインキ着肉性を低下させるという問題があった。
2.前記高分子化合物がパーフルオロアルキル基を実質的に含まないことを特徴とする前記1に記載の平版印刷版原版。
3.前記画像記録層が、赤外線吸収剤、ラジカル重合開始剤及びラジカル重合性化合物を含有することを特徴とする前記1又は前記2に記載の平版印刷版原版。
4.前記高分子化合物のアルキレンオキサイドの繰返し単位数が20~50であることを特徴とする前記1~前記3のいずれか1項に記載の平版印刷版原版。
5.前記高分子化合物が下記一般式(1)で表される構造を側鎖に有することを特徴とする前記1~前記4のいずれか1項に記載の平版印刷版原版。
7.前記画像記録層が、アンモニウム塩及びホスホニウム塩から選ばれる少なくともいずれかを含有することを特徴とする前記1~前記6のいずれか1項に記載の平版印刷版原版。
8.前記アンモニウム塩又はホスホニウム塩の対アニオンが有機ボレートアニオンであることを特徴とする前記7に記載の平版印刷版原版。
9.前記アンモニウム塩が、下記一般式(2)で表されることを特徴とする前記7又は前記8に記載の平版印刷版原版。
11.前記アンモニウム塩が、下記一般式(3)で表される繰返し単位を有するポリマーであることを特徴とする前記7又は8に記載の平版印刷版原版。
13.前記画像記録層が、露光後に、印刷機上で印刷インキ及び湿し水のうちの少なくともいずれかを供給して未露光部を除去することにより画像形成可能な画像記録層であることを特徴とする前記1~前記12のいずれか1項に記載の平版印刷版原版。
14.アルキレンオキサイドの繰返し単位数が10~120であるポリ(アルキレンオキサイド)部位を有する高分子化合物の含有量が画像記録層中の全固形分に対して10~90質量%であることを特徴とする前記1~前記13のいずれか1項に記載の平版印刷版原版。
本発明の平版印刷版原版は、支持体上に画像記録層、画像記録層上に保護層を有する。支持体と画像記録層の間に下塗り層を有してもよい。
以下、本発明の平版印刷版原版の構成要素及び成分などについて説明する。
本発明の平版印刷版原版は、画像記録層の上に保護層(オーバーコート層)を有する。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。
本発明の保護層としては、無機質の層状化合物を含有し、上記酸素低透過性のポリマーをバインダーとして用いることが好ましい。
一般式 A(B,C)2-5 D4 O10(OH,F,O)2
〔ただし、AはK,Na,Caの何れか、B及びCはFe(II),Fe(III),Mn,Al,Mg,Vの何れかであり、DはSi又はAlである。〕で表される天然雲母、合成雲母等の雲母群、式3MgO・4SiO・H2Oで表されるタルク、テニオライト、モンモリロナイト、サポナイト、ヘクトライト、リン酸ジルコニウムなどが挙げられる。
本発明の画像記録層は、(A)アルキレンオキサイドの繰返し単位数が10~120であるポリ(アルキレンオキサイド)部位を有する高分子化合物を含有することを特徴とする。これによって、良好な機上現像性と共に、良好な着肉性が得られる。以下では、ポリ(アルキレンオキサイド)部位を有する高分子化合物を特定高分子化合物とよぶ。
なお、特定高分子化合物が着肉性を改良する機構としては、次のように推測している。特定高分子化合物中のアルキレンオキサイド長鎖が、雲母などの無機質層状化合物表面と相互作用し、特定高分子化合物が無機質層状化合物表面を覆い、無機質層状化合物表面の親水性を低下させることにより、着肉性が改良される。
以下に、画像記録層に含有できる各成分について、順次説明する。
本発明の平版印刷版原版に用いられるアルキレンオキサイドの繰返し単位数が10~120である特定高分子化合物は、ポリ(アルキレンオキサイド)部位を主鎖に有していても、側鎖に有していてもよく、ポリ(アルキレンオキサイド)を側鎖に有するグラフトポリマーでも、ポリ(アルキレンオキサイド)含有ブロックと(アルキレンオキサイド)非含有の繰返し単位で構成されるブロックとのブロックコポリマーでもよい。
主鎖に有する場合にはポリウレタン樹脂が好ましい。側鎖に有する場合の主鎖のポリマーとしては、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、ポリウレア樹脂、ポリイミド樹脂、ポリアミド樹脂、エポキシ樹脂、メタクリル樹脂、ポリスチレン系樹脂、ノボラック型フェノール系樹脂、ポリエステル樹脂、合成ゴム、天然ゴムが挙げられるが、特にアクリル樹脂が好ましい。
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たものである。
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10~120であり、20~70の範囲が好ましく、20~50の範囲がより好ましい。
アルキレンオキサイドの繰り返し数が10未満だとインキ受容性の向上が得られない。また、繰り返し数が120を超えると摩耗による耐刷性、インキ受容性による耐刷性、両方が低下する。
上記の中でも、R1は水素原子又はメチル基が好ましく、水素原子が最も好ましい。R2は水素原子又はメチル基が最も好ましい。
分子の主鎖中にエチレン性不飽和結合を有するポリマーの例としては、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ポリマーの例としては、アクリル酸又はメタクリル酸のエステル又はアミドのポリマーであって、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ポリマーを挙げることができる。
アミド残基の具体例としては、-CH2 CH=CH2 、-CH2 CH2 -Y(式中、Yはシクロヘキセン残基を表す。)、-CH2 CH2 -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。
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ラジカル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である。
これらのうち好ましい赤外線吸収剤としては、シアニン色素、スクワリリウム色素、ピリリウム塩、ニッケルチオレート錯体が挙げられる。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。
ここで、R9及びR10は、それぞれ同じでも異なっていてもよく、置換基を有していてもよい炭素原子数6~10の芳香族炭化水素基、炭素原子数1~8のアルキル基、水素原子を表し、またR9とR10とが互いに結合して環を形成してもよい。なかでもフェニル基が好ましい。
X2は酸素原子又は硫黄原子を示し、L1は、炭素原子数1~12の炭化水素基、ヘテロ原子を有する芳香族環、ヘテロ原子を含む炭素原子数1~12の炭化水素基を示す。
なお、ここでヘテロ原子とは、N、S、O、ハロゲン原子、Seを示す。以下に示す基において、Xa-は後述するZa-と同様に定義され、Raは、水素原子、アルキル基、アリール基、置換又は無置換のアミノ基、ハロゲン原子より選択される置換基を表す。
これらの赤外線吸収剤は、1種のみを用いてもよいし、2種以上を併用してもよい。
本発明に用いられるラジカル重合開始剤は、光照射によりラジカルを発生する化合物である。発生したラジカルがラジカル重合性化合物を重合硬化させる。
また、米国特許第5,135,838号や米国特許第5,200,544号の明細書に記載されているベンジルスルホナート類、特開平2-100054号、特開平2-100055号及び特開平9-197671号の各公報に記載されている活性スルホン酸エステル、特開2008-001740号公報に記載のN-ヒドロキシイミド化合物のスルホン酸エステルなどのイミドエステル、特開昭61-166544号、特開2002-328465号公報等に記載のジスルホン化合物類、J.C.S. Perkin II (1979)1653-1660)、J.C.S.Perkin II (1979)156-162、Journal of Photopolymer Science and Technology(1995)202-232、特開2000-66385号公報、特開2000-80068号公報、特開2008-195018号公報に記載のオキシムエステル化合物、特開平7-271029号公報に記載されているハロアルキル置換されたs-トリアジン化合物が挙げられる。
本発明に用いることができるラジカル重合性化合物は、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とが好ましい。このような化合物群は当該産業分野において広く知られているものであり、本発明においてはこれらを特に限定無く用いることができる。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並びにそれらの(共)重合体などの化学的形態をもつ。
アルキレンオキサイドの繰返し単位数が10~120の特定高分子化合物の添加により本発明の平版印刷版原版のインキ着肉性を向上させることができるが、アンモニウム塩及びホスホニウム塩から選ばれる少なくともいずれかを併用することで、更に着肉性が良好となる。なかでも、アンモニウム塩を用いることが好ましい。保護層に無機質の層状化合物を含有させる場合、これらの化合物は、無機質の層状化合物の表面被覆剤として機能し、インキ着肉性の低下を防止する。
これらの基は更に同様の置換基で置換されていてもよい。
R12~R14は、全て同一でも、全て異なっていても、3つのうち2つが同一でもよい。
有機ボレートアニオンとしては、下記一般式(5)に示す構造を有する有機ボレートアニオンがより好ましい。対アニオンが有機ボレートアニオンである場合、高感度化に伴い画像部の硬化が更に進行し、水浸透性が抑制されるため、インキの着肉性を一段と向上させることができ、耐刷性が良好になる。
上記の中でも、R1~R4が置換基として電子吸引性基を有するアリール基であることが好ましい。アリール基に導入される好ましい電子吸引性基としては、ハロゲン原子、フルオロアルキル基が好ましく、なかでもフッ素原子、トリフルオロメチル基が好ましい。
その他の共重合成分を有する場合、高分子化合物中の一般式(3)で表される繰り返し単位の含有率は5~80モル%の範囲であることが好ましい。
30%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。この溶液をウベローデ還元粘度管(粘度計定数=0.010cSt/s)に入れ、30℃にて流れ落ちる時間を測定し、計算式(「動粘度」=「粘度計定数」×「液体が細管を通る時間(秒)」)を用いて定法により算出した。
(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)
(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)
(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)
(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)
(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)
(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20/80)
(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)
(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)
(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)
(10)N-2-(ブチルジメチルアンモニオ)エチルメタクリルアミド=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/メタクリルアミド共重合体(モル比20/40/40)
(11)4-(ブチルジメチルアンモニオメチル)スチレン=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(モル比20/80)
本発明では、機上現像性を向上させるため、疎水化前駆体を用いることができる。本発明における疎水化前駆体とは、熱が加えられたときに画像記録層を疎水性に変換できる微粒子を意味する。微粒子としては、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、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)から選ばれる少なくともひとつの粒子が好ましい。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。
このような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。その中で、より好適なものとして、ポリスチレン、ポリメタクリル酸メチルを挙げることができる。
本発明における画像記録層は、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ヒドロキシ類、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。
これらの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。
本発明の画像記録層には、機上現像性を促進するため、及び塗布面状を向上させるため界面活性剤を用いることができる。界面活性剤としては、ノニオン界面活性剤、アニオン界面活性剤、カチオン界面活性剤、両性界面活性剤、フッ素系界面活性剤等が挙げられる。界面活性剤は、単独で用いてもよく、2種以上を組み合わせて用いてもよい。界面活性剤にハロゲン化物イオンが不純物や対イオンとして含まれる場合は、脱塩、イオン交換などの方法で、除去又は他の陰イオンに交換することが好ましい。
本発明に用いられる両性界面活性剤は、特に限定されず、従来公知のものを用いることができる。例えば、カルボキシベタイン類、アミノカルボン酸類、スルホベタイン類、アミノ硫酸エステル類、イミタゾリン類が挙げられる。
界面活性剤の含有量は、画像記録層の全固形分に対して、0.01~10質量%であるのが好ましく、0.1~5質量%であるのがより好ましい。0.01質量%以上であれば界面活性能が十分に発揮され、塗布面状の均一性が得られる。また、含有量が10質量%以下であれば、画像記録層上に更に一層、例えば保護層などを塗布する場合に、塗布ハジキを生じず、良好な性能が得られる。
本発明における画像記録層には、必要に応じて、更に他の成分として、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、及び共増感剤若しくは連鎖移動剤などを添加することができる。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[0060]に記載の化合物及び添加量が好ましい。
本発明における画像記録層は、例えば、特開2008-195018号公報の段落番号[0142]~[0143]に記載のように、必要な上記各成分を公知の溶剤に分散又は溶解して塗布液を調製し、これを支持体上にバーコーター塗布など公知の方法で塗布し、乾燥することで形成される。塗布、乾燥後に得られる支持体上の画像記録層塗布量(固形分)は、用途によって異なるが、一般的に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。
本発明の平版印刷版原版は、画像記録層と支持体との間に下塗り層(中間層と呼ばれることもある)を設けることが好ましい。下塗り層は、露光部においては支持体と画像記録層との密着を強化し、未露光部においては画像記録層の支持体からのはく離を生じやすくさせるため、耐刷性を損なわず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。
下塗り層用の高分子樹脂は、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。
本発明の平版印刷版原版に用いられる支持体としては、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。
また、上記アルミニウム板は必要に応じて、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であるのが好ましい。
本発明の平版印刷版原版の製版は機上現像方法で行うことが好ましい。機上現像方法は、平版印刷版原版を画像露光する工程と、露光後の平版印刷版原版になんらの現像処理を施すことなく、油性インキと水性成分とを供給して、印刷する印刷工程とを有し、該印刷工程の途上において平版印刷版原版の未露光部分が除去されることを特徴とする。画像様の露光は平版印刷版原版を印刷機に装着した後、印刷機上で行ってもよいし、プレートセッターなどで別途行ってもよい。後者の場合は、露光済み平版印刷版原版は現像処理工程を経ないでそのまま印刷機に装着される。その後、該印刷機を用い、油性インキと水性成分とを供給してそのまま印刷することにより、印刷途上の初期の段階で機上現像処理、すなわち、未露光領域の画像記録層が除去され、それに伴って親水性支持体表面が露出され非画像部が形成される。油性インキ及び水性成分としては、通常の平版印刷用の印刷インキと湿し水が用いられる。
以下、更に詳細に説明する。
赤外線レーザーに関しては、出力は100mW以上であることが好ましく、1画素当たりの露光時間は20マイクロ秒以内であるのが好ましく、また照射エネルギー量は10~300mJ/cm2であるのが好ましい。レーザーにおいては、露光時間を短縮するためマルチビームレーザーデバイスを用いるのが好ましい。
このようにして、本発明の平版印刷版原版はオフセット印刷機上で機上現像され、そのまま多数枚の印刷に用いられる。
(1)支持体の作製(その1)
厚み0.3mmのアルミニウム板(材質JIS A 1050)の表面の圧延油を除去するため、10質量%アルミン酸ソーダ水溶液を用いて50℃で30秒間、脱脂処理を施した後、毛径0.3mmの束植ナイロンブラシ3本とメジアン径25μmのパミス-水懸濁液(比重1.1g/cm3)を用いアルミニウム表面を砂目立てして、水でよく洗浄した。この板を45℃の25質量%水酸化ナトリウム水溶液に9秒間浸漬してエッチングを行い、水洗後、更に60℃で20質量%硝酸に20秒間浸漬し、水洗した。この時の砂目立て表面のエッチング量は約3g/m2であった。
次に、この板に15質量%硫酸(アルミニウムイオンを0.5質量%含む)を電解液として電流密度15A/dm2で2.5g/m2の直流陽極酸化皮膜を設けた後、水洗、乾燥して支持体(1)を作製した。
その後、非画像部の親水性を確保するため、支持体(1)に2.5質量%3号ケイ酸ソーダ水溶液を用いて60℃で10秒間、シリケート処理を施し、その後、水洗して支持体(2)を得た。Siの付着量は10mg/m2であった。この基板の中心線平均粗さ(Ra)を直径2μmの針を用いて測定したところ、0.51μmであった。
次に、上記支持体(2)上に、下記下塗り層用塗布液(1)を乾燥塗布量が20mg/m2になるよう塗布して、以下の実験に用いる下塗り層を有する支持体を作製した。
・下記構造の下塗り層用化合物(1) 0.18g
・ヒドロキシエチルイミノ二酢酸 0.10g
・メタノール 55.24g
・水 6.15g
上記のようにして形成された下塗り層上に、下記組成の画像記録層塗布液(1)をバー塗布した後、100℃60秒でオーブン乾燥し、乾燥塗布量1.0g/m2の画像記録層を形成した。
画像記録層塗布液(1)は下記感光液(1)及びミクロゲル液(1)を塗布直前に混合し攪拌することにより得た。
・特定高分子化合物〔表1に本明細書例示化合物番号で記載〕
0.240g
・赤外線吸収染料(1)〔下記構造〕
0.030g
・ラジカル重合開始剤(1)〔下記構造〕
0.162g
・ラジカル重合性化合物
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)
0.192g
・低分子親水性化合物
トリス(2-ヒドロキシエチル)イソシアヌレート
0.062g
・低分子親水性化合物(1)〔下記構造〕
0.050g
・アンモニウム塩(表1記載の化合物) 表1記載の量
・フッ素系界面活性剤(1)〔下記構造〕
0.008g
・2-ブタノン
1.091g
・1-メトキシ-2-プロパノール
8.609g
・ミクロゲル(1) 2.640g
・蒸留水 2.425g
油相成分として、トリメチロールプロパンとキシレンジイソシアナート付加体(三井化学ポリウレタン(株)製、タケネートD-110N)10g、ペンタエリスリトールトリアクリレート(日本化薬(株)製、SR444)3.15g、及びパイオニンA-41C(竹本油脂(株)製)0.1gを酢酸エチル17gに溶解した。水相成分として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、これを前記ミクロゲル(1)とした。ミクロゲルの平均粒径を光散乱法により測定したところ、平均粒径は0.2μmであった。
上記画像記録層上に、更に下記組成の保護層塗布液(1)をバー塗布した後、120℃、60秒でオーブン乾燥し、乾燥塗布量0.15g/m2の保護層を形成して平版印刷版原版(1)~(12)〔実施例1~12用〕、及び平版印刷版原版(41)~(43)〔比較例1~3用〕を得た。
なお、平版印刷版原版(44)〔比較例4用〕は、上記保護層塗布液(1)の代わりに保護層塗布液(2)を使用した以外は平版印刷版原版1と同様にして作製した。
・無機質層状化合物分散液(1) 1.5g
・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 0.55g
・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
・日本エマルジョン(株)製界面活性剤
(エマレックス710)1質量%水溶液 0.86g
・イオン交換水 6.0g
イオン交換水193.6gに合成雲母ソマシフME-100(コープケミカル(株)製)6.4gを添加し、ホモジナイザーを用いて平均粒径(レーザー散乱法)が3μmになるまで分散した。得られた分散粒子のアスペクト比は100以上であった。
・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 0.55g
・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
・日本エマルジョン(株)製界面活性剤
(エマレックス710)1質量%水溶液 0.86g
・イオン交換水 6.0g
得られた平版印刷版原版を赤外線半導体レーザー搭載の富士フイルム(株)製Luxel PLATESETTER T-6000IIIにて、外面ドラム回転数1000rpm、レーザー出力70%、解像度2400dpiの条件で露光した。露光画像にはベタ画像及び20μmドットFMスクリーンの50%網点チャートを含むようにした。
得られた露光済み原版を現像処理することなく、(株)小森コーポレーション製印刷機LITHRONE26の版胴に取り付けた。Ecolity-2(富士フイルム(株)製)/水道水=2/98(容量比)の湿し水とValues-G(N)墨インキ(大日本インキ化学工業(株)製)とを用い、LITHRONE26の標準自動印刷スタート方法で湿し水とインキとを供給して機上現像した後、毎時10000枚の印刷速度で、特菱アート(76.5kg)紙に印刷を100枚行った。
画像記録層の未露光部の印刷機上での除去が完了し、非画像部にインキが転写しない状態になるまでに要した印刷用紙の枚数を機上現像性として計測した。結果を表1に示す。
上述した機上現像性の評価を行った後、更に印刷を続けた。印刷枚数を増やしていくと徐々に、画像記録層が磨耗するため印刷物上のインキ濃度が低下した。印刷物におけるFMスクリーン50%網点の網点面積率をグレタグ濃度計で計測した値が印刷100枚目の計測値よりも5%低下したときの印刷部数を刷了枚数として耐刷性を評価した。結果を表1に示す。
上述した機上現像性の評価を行った後、更に印刷を続けた。印刷枚数を増やしていくと徐々に、画像部のインキ受容性が低下し、印刷物上のインキ濃度が低下した。印刷物におけるFMスクリーン50%網点の網点面積率をグレタグ濃度計で計測した値が印刷100枚目の計測値よりも5%低下したときの印刷部数を刷了枚数として耐刷性を評価した。結果を表1に示す。ちなみに、インキ濃度の低下が磨耗によるものか、画像記録層のインキ受容性低下に伴うものかの識別は、インキ濃度低下後の印刷版をSEM観察し判別した。
(1)画像記録層の形成
下塗り層を有する上記の支持体に、下記の画像記録層塗布液(4)をバー塗布した後、70℃、60秒でオーブン乾燥し、乾燥塗布量0.6g/m2の画像記録層を作製し、画像記録層を形成した。
・特定高分子化合物〔表2記載〕 4.0g
・赤外線吸収染料(2)[下記構造] 0.2g
・光開始剤 Irgacure250(チバスペシャリティケミカルズ製)0.5g
・ラジカル重合性化合物 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 Chimie社製) 0.4g
・KlucelM(Hercules社製) 4.8g
・ELVACITE4026(Ineos Acrylica社製) 2.5g
・n-プロパノール 55.0g
・2-ブタノン 17.0g
・IRGACURE 250:(4-メトキシフェニル)[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)
上記画像記録層上に、更に前記の保護層塗布液(1)をバー塗布した後、120℃、60秒でオーブン乾燥し、乾燥塗布量0.15g/m2の保護層を形成して平版印刷版原版(21)~(29)〔実施例13~21用〕及び(45)~(46)〔比較例5~6用〕を得た。
なお、平版印刷版原版(47)〔比較例7用〕は、保護層塗布液(1)の代わりに保護層塗布液(2)を用いた以外は、平版印刷版原版(13)と同様にして作製した。
前記画像記録層塗布液(4)の特定高分子化合物の代わりに下記ポリマー微粒子水分散液(1)を用いた画像記録層塗布液(5)を使用した以外は平版印刷版原版(21)の作製と同様にして平版印刷版原版(30)〔実施例22用〕を得た。なお、ポリマー微粒子水分散液の添加量は、画像記録層塗布液(5)中、19.0gである。
1000mlの4つ口フラスコに撹拌機、温度計、滴下ロート、窒素導入管、還流冷却器を施し、窒素ガスを導入して脱酸素を行いつつ、ポリエチレングリコールメチルエーテルメタクリレート(PEGMA エチレングリコールの平均の繰返し単位は50)20g、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=18/9/73のポリマー微粒子水分散液(1)が得られた。このポリマー微粒子の粒径分布は、粒子径150nmに極大値を有していた。
平版印刷版原版(21)~(30)、(45)~(47)について、実施例1~12、及び比較例1~3と同様の評価を行った。結果を表2に示す。
前記画像記録塗布液(5)に、更に下記化合物(c1)0.3gを加えた画像記録層塗布液(6)を使用した以外は平版印刷版原版(21)の作製と同様にして平版印刷版原版(31)[実施例23用]を得た。
前記画像記録塗布液(5)に、更に下記化合物(d1)0.3gを加えた画像記録層塗布液(7)を使用した以外は平版印刷版原版(21)の作製と同様にして平版印刷版原版(32)[実施例24用]を得た。
平版印刷版原版(31)~(32)について、実施例1~12、及び比較例1~3と同様の評価を行った。結果を表3に示す。
本出願は、2009年3月30日出願の日本特許出願(特願2009-83710)、2009年9月1日出願の日本特許出願(特願2009-202013)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。
Claims (14)
- 支持体、画像記録層及び保護層をこの順に有する平版印刷版原版であって、保護層に無機質層状化合物を含有し、かつ、アルキレンオキサイドの繰返し単位数が10~120であるポリ(アルキレンオキサイド)部位を有する高分子化合物を画像記録層に含有することを特徴とする平版印刷版原版。
- 前記高分子化合物がパーフルオロアルキル基を実質的に含まないことを特徴とする請求項1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、ラジカル重合開始剤及びラジカル重合性化合物を含有することを特徴とする請求項1又は2に記載の平版印刷版原版。
- 前記高分子化合物のアルキレンオキサイドの繰返し単位数が20~50であることを特徴とする請求項1~3のいずれか1項に記載の平版印刷版原版。
- 前記無機質層状化合物が雲母であることを特徴とする請求項1~5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、アンモニウム塩及びホスホニウム塩から選ばれる少なくともいずれかを含有することを特徴とする請求項1~6のいずれか1項に記載の平版印刷版原版。
- 前記アンモニウム塩又はホスホニウム塩の対アニオンが有機ボレートアニオンであることを特徴とする請求項7に記載の平版印刷版原版。
- 前記一般式(2)において、R3~R6のうち少なくとも1つがアリール基又はアラルキル基であることを特徴とする請求項9に記載の平版印刷版原版。
- 前記一般式(3)において、L1がフェニレン基、カルボニルオキシ基及びカルボニルイミノ基から選ばれる少なくとも一つの基を有する連結基であることを特徴とする請求項11に記載の平版印刷版原版。
- 前記画像記録層が、露光後に、印刷機上で印刷インキ及び湿し水のうちの少なくともいずれかを供給して未露光部を除去することにより画像形成可能な画像記録層であることを特徴とする請求項1~12のいずれか1項に記載の平版印刷版原版。
- アルキレンオキサイドの繰返し単位数が10~120であるポリ(アルキレンオキサイド)部位を有する高分子化合物の含有量が画像記録層中の全固形分に対して10~90質量%であることを特徴とする請求項1~13のいずれか1項に記載の平版印刷版原版。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2010800150812A CN102378696A (zh) | 2009-03-30 | 2010-02-24 | 平版印刷版原版 |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2009083710 | 2009-03-30 | ||
JP2009-083710 | 2009-03-30 | ||
JP2009-202013 | 2009-09-01 | ||
JP2009202013A JP5183598B2 (ja) | 2009-03-30 | 2009-09-01 | 平版印刷版原版 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2010116808A1 true WO2010116808A1 (ja) | 2010-10-14 |
Family
ID=42936096
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2010/052891 WO2010116808A1 (ja) | 2009-03-30 | 2010-02-24 | 平版印刷版原版 |
Country Status (3)
Country | Link |
---|---|
JP (1) | JP5183598B2 (ja) |
CN (1) | CN102378696A (ja) |
WO (1) | WO2010116808A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016027843A1 (ja) * | 2014-08-21 | 2016-02-25 | 富士フイルム株式会社 | 下層膜形成用樹脂組成物、積層体、パターン形成方法、インプリント形成用キットおよびデバイスの製造方法 |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9177028B2 (en) * | 2012-04-30 | 2015-11-03 | International Business Machines Corporation | Deduplicating storage with enhanced frequent-block detection |
US9659060B2 (en) | 2012-04-30 | 2017-05-23 | International Business Machines Corporation | Enhancing performance-cost ratio of a primary storage adaptive data reduction system |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002116539A (ja) * | 2000-10-11 | 2002-04-19 | Fuji Photo Film Co Ltd | 平版印刷版原版 |
JP2007055224A (ja) * | 2005-01-26 | 2007-03-08 | Fujifilm Corp | 平版印刷版原版、平版印刷方法および平版印刷版原版の梱包体 |
EP2006738A2 (en) * | 2007-06-21 | 2008-12-24 | Fujifilm Corporation | Lithographic printing plate precursor and lithographic printing method |
JP2009029124A (ja) * | 2007-07-02 | 2009-02-12 | Fujifilm Corp | 平版印刷版原版、及びそれを用いた印刷方法 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009000976A (ja) * | 2007-06-25 | 2009-01-08 | Fujifilm Corp | 平版印刷版原版および平版印刷方法 |
JP2009056733A (ja) * | 2007-08-31 | 2009-03-19 | Fujifilm Corp | 平版印刷版原版および平版印刷方法 |
JP2009056717A (ja) * | 2007-08-31 | 2009-03-19 | Fujifilm Corp | 平版印刷版原版および平版印刷方法 |
-
2009
- 2009-09-01 JP JP2009202013A patent/JP5183598B2/ja not_active Expired - Fee Related
-
2010
- 2010-02-24 CN CN2010800150812A patent/CN102378696A/zh active Pending
- 2010-02-24 WO PCT/JP2010/052891 patent/WO2010116808A1/ja active Application Filing
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002116539A (ja) * | 2000-10-11 | 2002-04-19 | Fuji Photo Film Co Ltd | 平版印刷版原版 |
JP2007055224A (ja) * | 2005-01-26 | 2007-03-08 | Fujifilm Corp | 平版印刷版原版、平版印刷方法および平版印刷版原版の梱包体 |
EP2006738A2 (en) * | 2007-06-21 | 2008-12-24 | Fujifilm Corporation | Lithographic printing plate precursor and lithographic printing method |
JP2009029124A (ja) * | 2007-07-02 | 2009-02-12 | Fujifilm Corp | 平版印刷版原版、及びそれを用いた印刷方法 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016027843A1 (ja) * | 2014-08-21 | 2016-02-25 | 富士フイルム株式会社 | 下層膜形成用樹脂組成物、積層体、パターン形成方法、インプリント形成用キットおよびデバイスの製造方法 |
Also Published As
Publication number | Publication date |
---|---|
CN102378696A (zh) | 2012-03-14 |
JP2010253920A (ja) | 2010-11-11 |
JP5183598B2 (ja) | 2013-04-17 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5894905B2 (ja) | 新聞印刷用平版印刷版原版及びその製造方法、並びに平版印刷版の製版方法 | |
JP5828045B2 (ja) | 平版印刷版原版及び製版方法 | |
JP5789448B2 (ja) | 平版印刷版原版及びその製版方法 | |
JP5786099B2 (ja) | 平版印刷版原版及び平版印刷版の製版方法 | |
JP5277039B2 (ja) | 平版印刷版原版およびその製版方法 | |
JP5244987B2 (ja) | 平版印刷版原版及びその製版方法 | |
JP5651554B2 (ja) | 機上現像型平版印刷版原版及びそれを用いる製版方法 | |
JP2012176606A (ja) | 平版印刷版原版及びその製版方法 | |
US20110076618A1 (en) | Lithographic printing plate precursor and plate making method thereof | |
JP5183598B2 (ja) | 平版印刷版原版 | |
JP5746936B2 (ja) | 平版印刷版原版及びその製版方法 | |
US20100248138A1 (en) | Lithographic printing plate precursor | |
JP5439422B2 (ja) | 平版印刷版の製版方法 | |
WO2011118456A1 (ja) | 平版印刷版原版及びその製造方法 | |
JP5453023B2 (ja) | 印刷用湿し水及び平版印刷版の印刷方法 | |
WO2015064331A1 (ja) | 発色性組成物、平版印刷版原版及びその製版方法 | |
WO2014156449A1 (ja) | 平版印刷版原版及びその製版方法 | |
WO2015045789A1 (ja) | 平版印刷版原版及び製版方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201080015081.2 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 10761510 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 7114/CHENP/2011 Country of ref document: IN |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 10761510 Country of ref document: EP Kind code of ref document: A1 |