WO2015008578A1 - 平版印刷版原版及びその製版方法 - Google Patents
平版印刷版原版及びその製版方法 Download PDFInfo
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- WO2015008578A1 WO2015008578A1 PCT/JP2014/066440 JP2014066440W WO2015008578A1 WO 2015008578 A1 WO2015008578 A1 WO 2015008578A1 JP 2014066440 W JP2014066440 W JP 2014066440W WO 2015008578 A1 WO2015008578 A1 WO 2015008578A1
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- lithographic printing
- printing plate
- plate precursor
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C1/00—Forme preparation
- B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C1/00—Forme preparation
- B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
- B41C1/1008—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials
- B41C1/1025—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 using materials comprising a polymeric matrix containing a polymeric particulate material, e.g. hydrophobic heat coalescing particles
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
- B41C2210/04—Negative working, i.e. the non-exposed (non-imaged) areas are removed
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
- B41C2210/08—Developable by water or the fountain solution
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
- B41C2210/22—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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
- B41C2210/26—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
Definitions
- the present invention relates to a lithographic printing plate precursor and a plate making method thereof.
- the present invention relates to a lithographic printing plate precursor capable of image recording by various lasers and on-press development based on a digital signal, and a plate making method thereof.
- the lithographic printing plate is composed of an oleophilic image portion that receives ink in the printing process and a hydrophilic non-image portion 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 having a lipophilic photosensitive resin layer (image recording layer, image forming layer) on a hydrophilic support is used, and a mask such as a lithographic film is applied to the lithographic printing plate precursor.
- development processing with an alkaline developer or the like 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.
- CTP computer to plate
- a lithographic printing plate precursor suitable for on-press development is a lithographic printing plate precursor (hereinafter referred to as on-press development type) having an image recording layer from which a non-image portion can be removed by at least one of printing ink and dampening water on a printing press. It is also called a lithographic printing plate precursor).
- on-press development type lithographic printing plate precursor an infrared absorber, a polymerization initiator, a lithographic printing plate precursor (for example, Patent Document 1) having an image recording layer containing a polymerizable compound on a support, an infrared absorber,
- Patent Literature 2 having an image recording layer containing thermoplastic polymer particles on a support is known.
- an operation is performed to inspect and identify an image on the lithographic printing plate to check whether the image is recorded as intended.
- a colored image can be obtained by development processing if the image recording layer is colored, so it is easy to check the image before attaching the printing plate to the printing press. is there.
- Patent Document 3 describes a heat-sensitive imaging element containing an IR dye having a specific structure capable of forming a printout image by infrared rays or heat, and the heat-sensitive imaging element containing an IR dye having a specific structure includes: It is described that a visible image having high contrast can be formed after image exposure. However, it is recognized that the on-press developability of heat-sensitive imaging elements containing IR dyes of a specific structure is significantly reduced over time.
- Patent Document 3 Although the heat-sensitive image forming element described in Patent Document 3 is excellent in visibility (plate inspection), there is a problem that the on-press developability after storage is poor. Therefore, it is desired to provide a heat fusion type lithographic printing plate precursor excellent in visibility and on-press developability after aging.
- An object of the present invention is to provide a heat fusion type lithographic printing plate precursor having excellent visibility and having excellent on-press developability even after long-term storage of the lithographic printing plate precursor. Another object is to provide a heat fusion type lithographic printing plate precursor having excellent storage stability.
- a lithographic printing plate precursor having an image recording layer containing (A) a thermoplastic fine particle polymer, (B) an infrared absorbing dye, and (C) a polyglycerol compound on a support, the infrared absorbing dye Is an infrared absorbing dye represented by the following general formula (I), and the polyglycerol compound is a compound having at least three structural units represented by the following general formula (1) and general formula (2):
- a lithographic printing plate precursor having an image recording layer containing (A) a thermoplastic fine particle polymer, (
- R 1 represents a group represented by the following general formula (Ia).
- R 2 and R 3 each independently represent a hydrogen atom or an alkyl group, or represent an atomic group necessary for R 2 and R 3 to be connected to each other to form a cyclic structure.
- Ar 1 and Ar 2 each independently represent an atomic group necessary for forming a benzene ring or a naphthalene ring.
- Y 1 and Y 2 each independently represents a sulfur atom or a dialkylmethylene group.
- R 4 and R 5 each independently represents an alkyl group.
- R 6 , R 7 , R 8 and R 9 each independently represent a hydrogen atom or an alkyl group.
- Za represents a counter ion that neutralizes the charge.
- R 10 represents a hydrogen atom, an aliphatic hydrocarbon group, or a (hetero) aryl group, or represents an atomic group necessary for linking with Y to form a cyclic structure.
- L represents a single bond or a divalent linking group.
- X represents —CO—, —SO 2 — or —SO—.
- Y represents —R 11a , —OR 11b , —NR 12 R 13 or —CF 3 .
- R 11a represents a hydrogen atom, an aliphatic hydrocarbon group or a (hetero) aryl group.
- R 11b represents an aliphatic hydrocarbon group or a (hetero) aryl group.
- R 12 and R 13 each independently represent a hydrogen atom, an aliphatic hydrocarbon group or a (hetero) aryl group, or atoms necessary for R 12 and R 13 to be linked together to form a cyclic structure. Represents a group.
- A represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkylcarbonyl group having 2 to 5 carbon atoms.
- A represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkylcarbonyl group having 2 to 5 carbon atoms.
- (3) The lithographic printing plate precursor as described in (1) or (2) above, wherein in the general formula (Ia), X is —CO—.
- Y is —OR 11b and R 11b is an alpha-positioned aliphatic hydrocarbon group.
- the lithographic printing plate precursor as described in any one of (1) to (8) above is image-exposed with an infrared laser, and then printed on at least one of printing ink and fountain solution.
- a plate making method for removing unexposed portions of the image recording layer is described in any one of (1) to (8) above.
- a heat fusion type lithographic printing plate precursor having excellent visibility and excellent on-press developability even after long-term storage of the lithographic printing plate precursor can be obtained.
- a heat fusion type lithographic printing plate precursor having excellent storage stability can be obtained.
- (meth) acrylate means “at least one of acrylate and methacrylate.“ (Meth) acryloyl group ”,“ (meth) acrylic acid ”,“ (meth) acrylic resin ”and the like. Is the same.
- the lithographic printing plate precursor according to the invention is a lithographic printing plate precursor having an image recording layer containing (A) a thermoplastic fine particle polymer, (B) an infrared absorbing dye, and (C) a polyglycerol compound on a support.
- the infrared absorbing dye is an infrared absorbing dye represented by the following general formula (I)
- the polyglycerol compound is any one of the structural units represented by the following general formula (1) and general formula (2). It is a compound having 3 or more.
- R 1 represents a group represented by the following general formula (Ia).
- R 2 and R 3 each independently represent a hydrogen atom or an alkyl group, or represent an atomic group necessary for R 2 and R 3 to be connected to each other to form a cyclic structure.
- Ar 1 and Ar 2 each independently represent an atomic group necessary for forming a benzene ring or a naphthalene ring.
- Y 1 and Y 2 each independently represents a sulfur atom or a dialkylmethylene group.
- R 4 and R 5 each independently represents an alkyl group.
- R 6 , R 7 , R 8 and R 9 each independently represent a hydrogen atom or an alkyl group.
- Za represents a counter ion that neutralizes the charge.
- R 10 represents a hydrogen atom, an aliphatic hydrocarbon group, or a (hetero) aryl group, or represents an atomic group necessary for linking with Y to form a cyclic structure.
- L represents a single bond or a divalent linking group.
- X represents —CO—, —SO 2 — or —SO—.
- Y represents —R 11a , —OR 11b , —NR 12 R 13 or —CF 3 .
- R 11a represents a hydrogen atom, an aliphatic hydrocarbon group or a (hetero) aryl group.
- R 11b represents an aliphatic hydrocarbon group or a (hetero) aryl group.
- R 12 and R 13 each independently represent a hydrogen atom, an aliphatic hydrocarbon group or a (hetero) aryl group, or atoms necessary for R 12 and R 13 to be linked together to form a cyclic structure. Represents a group.
- A represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkylcarbonyl group having 2 to 5 carbon atoms.
- the lithographic printing plate precursor of the present invention can be prepared as a lithographic printing plate by on-press development on a printing machine after image exposure. The lithographic printing plate precursor according to the invention is described in detail below.
- the image recording layer in the lithographic printing plate precursor according to the invention contains (A) a thermoplastic fine particle polymer, (B) an infrared absorbing dye, and (C) a polyglycerol compound.
- A a thermoplastic fine particle polymer
- B an infrared absorbing dye
- C a polyglycerol compound
- the thermoplastic fine particle polymer contained in the image recording layer of the lithographic printing plate precursor according to the invention preferably has a glass transition temperature (Tg) of 60 ° C. to 250 ° C.
- the Tg of the thermoplastic fine particle polymer is more preferably from 70 ° C to 140 ° C, and further preferably from 80 ° C to 120 ° C.
- Examples of the thermoplastic fine particle polymer having a Tg of 60 ° C. or higher include Research Disclosure No. 1 of January 1992. 33303, JP-A-9-123387, JP-A-9-131850, JP-A-9-171249, JP-A-9-171250, and EP931647, and the like. it can.
- homopolymers or copolymers composed of monomers such as ethylene, styrene, vinyl chloride, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, vinylidene chloride, acrylonitrile, vinyl carbazole, or mixtures thereof Etc. can be illustrated.
- Preferred examples include polystyrene and polymethyl methacrylate.
- the average particle size of the thermoplastic fine particle polymer is preferably 0.005 to 2.0 ⁇ m. If the average particle size is too large, the resolution may be deteriorated, and if it is too small, the temporal stability may be deteriorated. This value is also applied as an average particle diameter when two or more thermoplastic fine particle polymers are mixed.
- the average particle diameter is more preferably 0.01 to 1.5 ⁇ m, particularly preferably 0.05 ⁇ m to 1.0 ⁇ m.
- the polydispersity when two or more thermoplastic fine particle polymers are mixed is preferably 0.2 or more. The average particle size and polydispersity are calculated by laser light scattering.
- thermoplastic fine particle polymers Two or more kinds may be mixed and used. Specifically, at least two kinds of uses having different particle sizes or at least two kinds of uses having different Tg may be mentioned. By using two or more types in combination, the film curability of the image area is further improved, and the printing durability is further improved when a lithographic printing plate is used. For example, when thermoplastic particles having the same particle size are used as the thermoplastic fine particle polymer, there will be a certain amount of voids between the thermoplastic fine particle polymers, and even if the thermoplastic fine particle polymer is melted and solidified by image exposure, Curability may not be as desired.
- thermoplastic fine particle polymer having a different particle size when used, the porosity between the thermoplastic fine particle polymers can be lowered, and as a result, the film curability of the image area after image exposure can be reduced. Can be improved.
- thermoplastic fine particle polymer when the same Tg is used as the thermoplastic fine particle polymer, when the temperature rise of the image recording layer due to image exposure is insufficient, the thermoplastic fine particle polymer is not sufficiently melted and solidified, and the curability of the film is desired. It may not be a thing. In contrast, when a thermoplastic fine particle polymer having a different Tg is used, the film curability of the image area can be improved even when the temperature rise of the image recording layer due to image exposure is insufficient.
- thermoplastic fine particle polymer having different Tg is preferably 60 ° C. or higher.
- the difference of Tg is 10 degreeC or more, More preferably, it is 20 degreeC or more.
- the thermoplastic fine particle polymer having a Tg of 60 ° C. or higher is contained in an amount of 70% by mass or more based on the total thermoplastic fine particle polymer.
- the thermoplastic fine particle polymer may have a crosslinkable group.
- the crosslinkable group is thermally reacted by the heat generated in the image exposed area to form a crosslink between the polymers, and the film strength of the image area is increased and the printing durability is increased. Will be better.
- the crosslinkable group may be any functional group capable of performing any reaction as long as a chemical bond is formed.
- an ethylenically unsaturated group that performs a polymerization reaction for example, acryloyl group, methacryloyl group, vinyl group, allyl group, etc.
- An isocyanate group that performs an addition reaction, or a block thereof and a group having an active hydrogen atom that is a reaction partner for example, an amino group, a hydroxy group, a carboxyl group, etc.
- an epoxy group that also performs an addition reaction, and a reaction partner thereof
- examples thereof include an amino group, a carboxyl group or a hydroxy group, a carboxyl group and a hydroxy group or an amino group that perform a condensation reaction, an acid anhydride that performs a ring-opening addition reaction, an amino group or a hydroxy group, and the like.
- thermoplastic fine particle polymer having a crosslinkable group examples include acryloyl group, methacryloyl group, vinyl group, allyl group, epoxy group, amino group, hydroxy group, carboxyl group, isocyanate group, acid anhydride and the like.
- examples thereof include those having a crosslinkable group such as a group in which the above is protected.
- the introduction of these crosslinkable groups into the polymer may be performed during the polymerization of the fine particle polymer, or may be performed using a polymer reaction after the polymerization of the fine particle polymer.
- a crosslinkable group is introduced during the polymerization of the fine particle polymer, it is preferable to carry out emulsion polymerization or suspension polymerization of the monomer having a crosslinkable group.
- the monomer having a crosslinkable group include allyl methacrylate, allyl acrylate, vinyl methacrylate, vinyl acrylate, glycidyl methacrylate, glycidyl acrylate, 2-isocyanate ethyl methacrylate, or a block isocyanate based on alcohol thereof, 2-isocyanate ethyl acrylate or the like.
- Examples of the polymer reaction used when the crosslinkable group is introduced after the polymerization of the fine particle polymer include the polymer reaction described in WO96 / 34316.
- the thermoplastic fine particle polymer may react with each other through a crosslinkable group, or may react with a high molecular compound or a low molecular compound added to the image recording layer.
- the content of the thermoplastic fine particle polymer is preferably 40 to 95% by mass, more preferably 50 to 90% by mass, and particularly preferably 60 to 85% by mass based on the solid content of the image recording layer.
- the infrared absorbing dye contained in the image recording layer of the lithographic printing plate precursor according to the invention is an infrared absorbing dye represented by the following general formula (I).
- R 1 represents a group represented by the following general formula (Ia).
- R 2 and R 3 each independently represent a hydrogen atom or an alkyl group, or represent an atomic group necessary for R 2 and R 3 to be connected to each other to form a cyclic structure.
- Ar 1 and Ar 2 each independently represent an atomic group necessary for forming a benzene ring or a naphthalene ring.
- Y 1 and Y 2 each independently represents a sulfur atom or a dialkylmethylene group.
- R 4 and R 5 each independently represents an alkyl group.
- R 6 , R 7 , R 8 and R 9 each independently represent a hydrogen atom or an alkyl group.
- Za represents a counter ion that neutralizes the charge.
- R 10 represents a hydrogen atom, an aliphatic hydrocarbon group, or a (hetero) aryl group, or represents an atomic group necessary for linking with Y to form a cyclic structure.
- L represents a single bond or a divalent linking group.
- X represents —CO—, —SO 2 — or —SO—.
- Y represents —R 11a , —OR 11b , —NR 12 R 13 or —CF 3 .
- R 11a represents a hydrogen atom, an aliphatic hydrocarbon group or a (hetero) aryl group.
- R 11b represents an aliphatic hydrocarbon group or a (hetero) aryl group.
- R 12 and R 13 each independently represent a hydrogen atom, an aliphatic hydrocarbon group or a (hetero) aryl group, or atoms necessary for R 12 and R 13 to be linked together to form a cyclic structure. Represents a group.
- the term “(hetero) aryl group” is used as a general term for an aryl group and a heteroaryl group.
- the infrared absorbing dye represented by the general formula (I) has a structural feature that R 1 is a group represented by the general formula (Ia). Due to this structural feature, the lithographic printing plate precursor containing the infrared absorbing dye represented by the general formula (I) exhibits extremely excellent image visibility by image exposure with infrared rays. That is, when the lithographic printing plate precursor containing the infrared absorbing dye represented by the general formula (I) is image-exposed with infrared rays, the group represented by the general formula (Ia) is decomposed to produce an amino group, which absorbs infrared rays. The dye changes to a colored body. As a result, the exposed portion is colored and a density difference is produced between the exposed portion and the unexposed portion, and the visibility of the image portion is improved.
- the alkyl group represented by R 2 or R 3 is preferably an alkyl group having 12 or less carbon atoms.
- the ring formed by connecting R 2 and R 3 is preferably a 5-membered ring or a 6-membered ring.
- the benzene ring or naphthalene ring represented by Ar 1 or Ar 2 may have a substituent, and examples of the substituent include an alkyl group having 12 or less carbon atoms, a halogen atom, and 12 or less carbon atoms. An alkoxy group etc. are mentioned.
- the alkyl group represented by R 4 or R 5 is preferably an alkyl group having 20 or less carbon atoms.
- the alkyl group may have a substituent, and examples of the substituent include an alkoxy group having 12 or less carbon atoms, a carboxyl group, and a sulfo group.
- the alkyl group represented by R 6 , R 7 , R 8 or R 9 is preferably an alkyl group having 12 or less carbon atoms.
- the counter anion that neutralizes the charge represented by Za is preferably a halide ion, a perchlorate ion, a tetrafluoroborate ion, a hexafluorophosphate ion, or a sulfonate ion, more preferably a perchlorate ion, Hexafluorophosphate ion or aryl sulfonate ion.
- Za is not necessary when the infrared absorbing dye represented by the general formula (I) has an anionic substituent in its structure and charge neutralization is not necessary.
- the aliphatic hydrocarbon group represented by R 10 includes an alkyl group, an alkenyl group, an alkynyl group, and the like.
- the number of carbon atoms in the aliphatic hydrocarbon group is preferably 40 or less, and more preferably 20 or less.
- the aliphatic hydrocarbon group may have a substituent, and examples of the substituent include a halogen atom, an alkoxy group, and an aryl group.
- the aryl group represented by R 10 may contain a single ring or a condensed ring of two or more rings. Specific examples include a phenyl group, an indenyl group, an ⁇ -naphthyl group, a ⁇ -naphthyl group, a fluorenyl group, a phenanthrenyl group, an anthracenyl group, and a pyrenyl group. As the aryl group, a phenyl group and a naphthyl group are preferable.
- the aryl group may have a substituent, and examples of the substituent include an alkyl group having 20 or less carbon atoms, a halogen atom, an alkoxy group, and an aryl group.
- the alkyl group may further have a substituent, and examples of the substituent include an alkoxy group, a carboxyl group, and a sulfo group.
- the heteroaryl group represented by R 10 preferably contains any one of an oxygen atom, a nitrogen atom, a sulfur atom, and a selenium atom as a hetero atom.
- the hetero atom is more preferably an oxygen atom, a nitrogen atom, or a sulfur atom, and particularly preferably an oxygen atom or a nitrogen atom.
- the heteroaryl group may have a substituent, and examples of the substituent include those exemplified as the substituent that the aryl group may have.
- R 10 is preferably an alkyl group having 40 or less carbon atoms which may be substituted or an aryl group which may be substituted from the viewpoint of improving visibility, and having 20 or less carbon atoms which may be substituted.
- An alkyl group is more preferred.
- the aliphatic hydrocarbon group represented by R 11a or R 11b includes an alkyl group, an alkenyl group, an alkynyl group, and the like.
- the number of carbon atoms in the aliphatic hydrocarbon group is preferably 40 or less, and more preferably 20 or less.
- the aliphatic hydrocarbon group may have a substituent, and examples of the substituent include a halogen atom, an alkoxy group, and an aryl group.
- the aryl group represented by R 11a or R 11b may contain a single ring or may contain a condensed ring of two or more rings. Specific examples include a phenyl group, an indenyl group, an ⁇ -naphthyl group, a ⁇ -naphthyl group, a fluorenyl group, a phenanthrenyl group, an anthracenyl group, and a pyrenyl group. As the aryl group, a phenyl group and a naphthyl group are preferable.
- the aryl group may have a substituent, and examples of the substituent include an alkyl group having 20 or less carbon atoms, a halogen atom, an alkoxy group, and an aryl group.
- the alkyl group may further have a substituent, and examples of the substituent include an alkoxy group, a carboxyl group, and a sulfo group.
- the heteroaryl group represented by R 11a or R 11b preferably contains an oxygen atom, a nitrogen atom, a sulfur atom, or a selenium atom as a hetero atom.
- the hetero atom is more preferably an oxygen atom, a nitrogen atom, or a sulfur atom, and particularly preferably an oxygen atom or a nitrogen atom.
- the heteroaryl group may have a substituent, and examples of the substituent include those exemplified as the substituent that the aryl group may have.
- R 11b is preferably an alpha-branched aliphatic hydrocarbon group, more preferably a secondary or tertiary aliphatic hydrocarbon group, particularly preferably a tertiary butyl group, from the viewpoint of improving visibility. It is.
- the aliphatic hydrocarbon group represented by R 12 or R 13 includes an alkyl group, an alkenyl group, an alkynyl group, and the like.
- the number of carbon atoms in the aliphatic hydrocarbon group is preferably 40 or less, and more preferably 20 or less.
- the aliphatic hydrocarbon group may have a substituent, and examples of the substituent include a halogen atom, an alkoxy group, and an aryl group.
- the aryl group represented by R 12 or R 13 may contain a single ring or may contain two or more condensed rings. Specific examples include a phenyl group, an indenyl group, an ⁇ -naphthyl group, a ⁇ -naphthyl group, a fluorenyl group, a phenanthrenyl group, an anthracenyl group, and a pyrenyl group. As the aryl group, a phenyl group and a naphthyl group are preferable.
- the aryl group may have a substituent, and examples of the substituent include an alkyl group having 20 or less carbon atoms, a halogen atom, an alkoxy group, and an aryl group.
- the alkyl group may further have a substituent, and examples of the substituent include an alkoxy group, a carboxyl group, and a sulfo group.
- the heteroaryl group represented by R 12 or R 13 preferably contains any one of an oxygen atom, a nitrogen atom, a sulfur atom, and a selenium atom as a hetero atom.
- the hetero atom is more preferably an oxygen atom, a nitrogen atom, or a sulfur atom, and particularly preferably an oxygen atom or a nitrogen atom.
- the heteroaryl group may have a substituent, and examples of the substituent include those exemplified as the substituent that the aryl group may have.
- the ring formed by connecting R 12 and R 13 is a nitrogen-containing heterocyclic ring.
- the nitrogen-containing heterocycle may have a substituent, and examples thereof include those exemplified as the substituent that the aryl group may have.
- the nitrogen-containing heterocyclic ring is a monocyclic, bicyclic or tricyclic ring which may contain 1 to 6 heteroatoms selected from nitrogen atom, oxygen atom and sulfur atom in addition to the nitrogen atom to which R 12 and R 13 are bonded. Represents a cyclic heterocycle.
- the nitrogen-containing heterocycle for example, a 3- to 15-membered nitrogen-containing unsaturated monocyclic, bicyclic or tricyclic heterocyclic ring ”, a 3- to 15-membered nitrogen-containing saturated monocyclic, bicyclic or tricyclic heterocyclic ring, etc. Can be mentioned.
- the nitrogen-containing heterocycle is preferably a 5- to 10-membered nitrogen-containing heterocycle.
- pyrrole imidazole, triazole, tetrazole, pyrazole, azepine, diazepine, indole, isoindole, indazole, purine, benzimidazole, benzotriazole, pyrroline, imidazoline , Triazoline, tetrazoline, pyrazoline, dihydropyridine, tetrahydropyridine, dihydropyrazine, tetrahydropyrazine, dihydropyrimidine, tetrahydropyrimidine, dihydropyridazine, tetrahydropyridazine, dihydroazepine, tetrahydroazepine, dihydrodiazepine, tetrahydrodiazepine, dihydrooxazole, dihydroisoxazole , Dihydr
- Examples of 5- to 10-membered nitrogen-containing saturated heterocycle include pyrrolidine, imidazolidine, triazolidine, tetrazolidine, pyrazolidine, piperidine, piperazine, perhydropyrimidine, perhydropyridazine, perhydroazepine, perhydrodiazepine, perhydroazocine , Tetrahydrooxazole (oxazolidine), tetrahydroisoxazole (isoxazolidine), tetrahydrothiazole (thiazolidine), tetrahydroisothiazole (isothiazolidine), tetrahydrofurazan, tetrahydrooxadiazole (oxadiazolidine), tetrahydrooxazine, tetrahydrooxadiazine, Perhydrooxazepine, perhydrooxadiazepine, tetrahydrothiadiazole (thiadiazolidine), tet Hydrothiazin
- R 12 and R 13 are preferably an alkyl group having 40 or less carbon atoms which may be substituted or an aryl group which may be substituted from the viewpoint of improving visibility, and the number of carbon atoms which may be substituted.
- An alkyl group of 20 or less is more preferable.
- the divalent linking group represented by L includes a divalent linking group comprising an alkylene group, an arylene group, —CO—, —O—, —NH—, and a combination of these groups.
- the number of carbon atoms contained in the divalent linking group is preferably 20 or less.
- L is preferably a single bond or a divalent linking group composed of a combination of two or more selected from an alkylene group, —CO—, —O—, and —NH—.
- a divalent linking group comprising a combination of two or more selected from an alkylene group of 8 or less, —CO—, —O—, and —NH— is more preferable.
- the group represented by R 1 is preferably a group that is decomposed by image exposure with infrared rays from the viewpoint of improving visibility.
- the group capable of decomposing by image exposure with infrared rays a group decomposing thermally upon image exposure is preferable.
- X in the general formula (Ia) is —CO—, —SO— or —SO 2 —.
- X is preferably —CO— or —SO—.
- X is particularly preferably —CO— from the viewpoint of excellent visibility in the present invention and the effect of maintaining excellent on-press developability even after long-term storage of a lithographic printing plate precursor. preferable.
- Y is preferably —OR 11b , where R 11b is preferably an alpha-position branched aliphatic hydrocarbon group, more preferably a secondary or tertiary group.
- R 11b is preferably an alpha-position branched aliphatic hydrocarbon group, more preferably a secondary or tertiary group.
- the infrared absorbing dye represented by the general formula (I) is synthesized by a known method. For example, it can be synthesized with reference to the description in JP-T-2008-544322.
- the content of the infrared absorbing dye represented by the general formula (I) is preferably 0.25 to 50% by mass, preferably 0.5 to 30% by mass, and 0.7 to 20% by mass based on the solid content of the image recording layer. Is particularly preferred.
- infrared absorbing dye represented by the general formula (I) used in the present invention are listed below, but the present invention is not limited to these.
- polyglycerol compound contained in the image recording layer of the lithographic printing plate precursor according to the invention is a compound having three or more structural units represented by the following general formula (1) and general formula (2).
- A represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkylcarbonyl group having 2 to 5 carbon atoms.
- a hydrogen atom, a methyl group, an ethyl group, a methylcarbonyl group or an ethylcarbonyl group is preferable, and a hydrogen atom is particularly preferable.
- the number of structural units represented by the general formulas (1) and (2) in the polyglycerol compound is preferably 3 to 500, more preferably 3 to 200, still more preferably 3 to 100, and particularly preferably 6 to 60. preferable.
- the hydroxyl value of the polyglycerol compound is preferably 670 to 1100, more preferably 770 to 1100.
- the hydroxyl value is the number of mg of potassium hydroxide required to neutralize acetic acid bonded to a hydroxyl group when 1 g of the polyglycerol compound is acetylated.
- the polyglycerol compound may be a linear compound or a branched compound.
- a in the general formula (1) or the general formula (2) becomes a single bond, and the structural unit represented by the general formula (1) or the general formula (2) is bonded to the branched compound. It has the structure which forms.
- the polyglycerol compound includes a structural unit represented by the following (a) or (b) (where O * represents a position to which the branched chain is bonded).
- the polyglycerol compound may contain a cyclic structural unit containing a hydrogen atom, for example, a structural unit represented by the following (c).
- the terminal structure of the polyglycerol compound is any one of a hydroxy group, an alkoxy group having 1 to 4 carbon atoms, or an alkylcarbonyloxy group having 2 to 5 carbon atoms. It is preferable that all terminal structures are hydroxy groups.
- the polyglycerol compound is substantially composed only of the structural units represented by the general formula (1) and the general formula (2), has a large number of hydroxy groups, and some of the hydroxy groups have 4 or less carbon atoms. Even when it is substituted with an alkyl group or an alkylcarbonyl group having 5 or less carbon atoms, the polyglycerol compound has extremely high hydrophilicity and does not substantially exhibit a surface-active effect. For this reason, during on-press development, the fountain solution does not penetrate into the exposed area (image area) of the image recording layer, thereby reducing the hydrophobicity and film strength of the image area. Good printability can be maintained.
- the polyglycerol compound is synthesized by a known method.
- polyglycerin ester Sakamoto Yakuhin Kogyo Co., Ltd., published in 1994
- polyglycerin # 310 polyglycerin # 500, polyglycerin # 750 (manufactured by Sakamoto Pharmaceutical Co., Ltd.), polyglycerin (manufactured by Yokkaichi Synthesis Co., Ltd.), polyglycerin PGL 06, polyglycerin PGL 10, polyglycerin PGL X (manufactured by Daicel Corporation) and the like.
- the content of the polyglycerol compound is preferably from 0.1 to 30% by mass, more preferably from 0.5 to 20% by mass, based on the solid content of the image recording layer.
- polyglycerol compound used in the present invention is listed below, but the present invention is not limited to these.
- the image recording layer of the lithographic printing plate precursor according to the invention contains a polyglycerol compound together with the infrared absorbing dye represented by the general formula (I).
- the infrared absorbing dye represented by the general formula (I) in the image recording layer of the lithographic printing plate precursor, the visibility is remarkably improved as described above.
- the on-press developability tends to deteriorate with time. This tendency becomes more prominent as the infrared absorbing dye has better visibility. This phenomenon is considered to be caused by the gradual decomposition of the infrared absorbing dye represented by the general formula (I) during storage of the lithographic printing plate precursor.
- the infrared absorbing dye represented by the general formula (I) is decomposed during storage of the lithographic printing plate precursor to generate a decomposition product such as a gas, and this decomposition product is in the image recording layer or between the image recording layer and the support. It is thought that the accumulation of dampening water is delayed during on-press development due to accumulation in the meantime. On the other hand, deterioration of on-press developability with time can be suppressed by using a polyglycerol compound in combination.
- the present invention since deterioration of on-press developability over time can be suppressed, both excellent visibility and excellent on-press developability are possible even after storage of a lithographic printing plate precursor. It becomes. In addition, contamination of the non-image area after storage can be suppressed. Further, the polyglycerol compound has high hydrophilicity and does not substantially exhibit a surface active action. For this reason, during on-press development, the fountain solution does not penetrate into the exposed area (image area) of the image recording layer, thereby reducing the hydrophobicity and film strength of the image area. It is possible to maintain good printability.
- the image recording layer of the present invention can contain a hydrophilic resin.
- the hydrophilic resin include hydrophilic groups such as hydroxy group, hydroxyethyl group, hydroxypropyl group, amino group, aminoethyl group, aminopropyl group, carboxyl group, carboxylate group, sulfo group, sulfonate group, and phosphate group.
- the resin it has is preferable.
- hydrophilic resins include gum arabic, casein, gelatin, starch derivatives, carboxymethylcellulose and its sodium salt, cellulose acetate, sodium alginate, vinyl acetate-maleic acid copolymers, styrene-maleic acid copolymers, polyacrylic acids and Salts thereof, polymethacrylic acids and salts thereof, homopolymers and copolymers of hydroxyethyl methacrylate, homopolymers and copolymers of hydroxyethyl acrylate, homopolymers and copolymers of hydroxypropyl methacrylate, homopolymers and copolymers of hydroxypropyl acrylate, hydroxybutyl Methacrylate homopolymers and copolymers, hydroxybutyl acrylate homopolymers and copolymers, polyesters Lenglycols, hydroxypropylene polymers, polyvinyl alcohols, hydrolyzed polyvinyl acetate having a degree of hydrolysis of at least 60%,
- the molecular weight of the hydrophilic resin is preferably 2000 or more. If it is less than 2000, sufficient film strength and printing durability cannot be obtained, which is not preferable.
- the content of the hydrophilic resin is preferably 0.5 to 30% by mass, more preferably 0.7 to 20% by mass based on the solid content of the image recording layer.
- Inorganic fine particles may be added to the image recording layer of the present invention.
- Preferred examples of the inorganic fine particles include silica, alumina, magnesium oxide, titanium oxide, magnesium carbonate, calcium alginate, and a mixture thereof.
- the inorganic fine particles are useful for preventing scratches during conveyance and processing due to strengthening of the coating and roughening of the surface, and preventing collapse of the load during loading.
- the average particle size of the inorganic fine particles is preferably 5 nm to 10 ⁇ m, more preferably 10 nm to 1 ⁇ m. Within this range, it is possible to form a non-image portion having excellent hydrophilicity that is stably dispersed with the thermoplastic fine particle polymer, sufficiently retains the film strength of the image recording layer, and hardly causes printing stains.
- the inorganic fine particles can be easily obtained as a commercial product such as a colloidal silica dispersion.
- the content of the inorganic fine particles is preferably 1.0 to 70% by mass, more preferably 5.0 to 50% by mass, based on the solid content of the image recording layer.
- a plasticizer can be added to the image recording layer of the present invention, if necessary, in order to impart flexibility of the coating film.
- the plasticizer include polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, and the like. It is done.
- a compound that initiates or accelerates the reaction of the heat-reactive functional group (crosslinkable group) as necessary can be added.
- the compound that initiates or accelerates the reaction of the thermoreactive functional group include compounds that generate radicals or cations by heat. Examples thereof include lophine dimer, trihalomethyl compound, peroxide, azo compound, diazonium salt, onium salt including diphenyliodonium salt, acylphosphine, imide sulfonate and the like.
- the amount of such a compound added is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, and particularly preferably 0.8 to 20% by mass based on the solid content of the image recording layer. Within this range, good reaction initiation or acceleration effect can be obtained without impairing on-press developability.
- the image recording layer of the present invention may contain an anionic surfactant for the purpose of ensuring the uniformity of application of the image recording layer.
- the anionic surfactant is not particularly limited as long as the above purpose is achieved. Among these, alkylbenzenesulfonic acid or a salt thereof, alkylnaphthalenesulfonic acid or a salt thereof, (di) alkyldiphenyl ether (di) sulfonic acid or a salt thereof, or an alkyl sulfate ester salt is preferable.
- the addition amount of the anionic surfactant is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the solid content of the image recording layer. In view of the above, 0.1 to 10% by mass is particularly preferable.
- the image recording layer of the present invention is formed by preparing or applying a coating solution by dissolving or dispersing the necessary components described above in a suitable solvent and coating the support.
- a suitable solvent water or a mixed solvent of water and an organic solvent is used, and mixed use of water and an organic solvent is preferable in terms of improving the surface state after coating.
- the amount of the organic solvent varies depending on the type of the organic solvent, and cannot be generally specified, but is usually preferably 5 to 50% by volume in the mixed solvent. However, it is necessary to use the organic solvent in such an amount that the thermoplastic fine particle polymer does not aggregate.
- the solid content concentration of the image recording layer coating solution is preferably 1 to 50% by mass.
- the organic solvent used as the solvent for the coating solution is preferably an organic solvent that is soluble in water.
- alcohol solvents such as methanol, ethanol, propanol, isopropanol, 1-methoxy-2-propanol, ketone solvents such as acetone and methyl ethyl ketone, glycol ether solvents such as ethylene glycol dimethyl ether, ⁇ -butyrolactone, N, N—
- Examples include dimethylformamide, N, N-dimethylacetamide, tetrahydrofuran, dimethyl sulfoxide and the like.
- an organic solvent having a boiling point of 120 ° C. or less and a solubility in water (amount dissolved in 100 g of water) of 10 g or more is preferable, and an organic solvent of 20 g or more is more preferable.
- the coating amount (solid content) of the image recording layer on the support obtained after coating and drying varies depending on the use, but is generally preferably 0.3 to 5.0 g / m 2 , and preferably 0.3 to 3. 0 g / m 2 is more preferable.
- the lithographic printing plate precursor according to the invention preferably has an intermediate layer containing a compound having a phosphoric acid group or a phosphonic acid group between the support and the image recording layer.
- an intermediate layer containing a compound having a phosphoric acid group or a phosphonic acid group between the support and the image recording layer.
- the compound having a phosphoric acid group or a phosphonic acid group introduced into the intermediate layer may have a salt structure, and may be an inorganic salt or an organic salt.
- an inorganic salt an alkali metal salt is preferable, and a sodium salt, a lithium salt, or a potassium salt is particularly preferable.
- an organic salt an ammonium salt is preferable, and a quaternary ammonium salt is particularly preferable.
- Examples of the compound having a phosphoric acid group or a phosphonic acid group include phosphoric acid, phosphonic acid, phosphoric ester, alkylphosphonic acid, and salts thereof.
- the phosphoric acid ester is preferably a compound represented by the following general formula (P1) or general formula (P2). These compounds may have a salt structure as described above.
- R 1 represents an alkyl group, preferably an alkyl group having 1 to 6 carbon atoms.
- the alkyl group may have a substituent, and examples of the substituent include a carboxyl group and a hydroxy group.
- R 2 represents an alkylene group, preferably an alkylene group having 1 to 8 carbon atoms.
- the alkylene group may have a substituent, and examples of the substituent include a carboxyl group and a hydroxy group.
- the alkylphosphonic acid is preferably a compound represented by the following general formula (P3) or general formula (P4). These compounds may have a salt structure as described above.
- R 1 represents an alkyl group or an alkenyl group, preferably an alkyl group or alkenyl group having 1 to 6 carbon atoms, and particularly preferably a methyl group or an ethyl group.
- the alkyl group may have a substituent, and examples of the substituent include a carboxyl group and a hydroxy group.
- R 2 represents an alkyl group, preferably an alkylene group having 1 to 8 carbon atoms, and particularly preferably a methylene group.
- Alkylene may have a substituent, and examples of the substituent include a carboxyl group and a hydroxy group.
- the compound having a phosphoric acid group or a phosphonic acid group is preferably a polymer compound.
- the high molecular compound which has a repeating unit which has a phosphoric acid group or a phosphonic acid group is mentioned.
- a polymer compound having a phosphoric acid group or a phosphonic acid group in the intermediate layer even after storing the lithographic printing plate precursor, stains on the non-image area (background stain) are suppressed and printing durability is improved. A further effect is obtained.
- the mass average molecular weight of the polymer compound is preferably 20,000 or more from the viewpoint of increasing these effects.
- the repeating unit having a phosphate group is preferably a repeating unit represented by the following general formula (P5), and the repeating unit having a phosphonic acid group is preferably a repeating unit represented by the following general formula (P6).
- A represents a hydrogen atom or a methyl group
- n represents an integer of 0 to 30.
- the compound having a phosphoric acid group or a phosphonic acid group may further have a hydrophilic group.
- a polymer compound having a repeating unit having a hydrophilic group represented by the following general formula (P7) in addition to the repeating unit having a phosphoric acid group or a phosphonic acid group is preferable.
- W represents a hydrophilic group and Y represents a divalent linking group.
- examples of the hydrophilic group represented by W include a sulfonic acid group or a salt thereof, a hydroxy group, a polyoxyalkylene group, an amide group, a carboxylic acid or a salt thereof, and the like.
- examples of the salt include an alkali metal salt (preferably sodium salt, lithium salt or potassium salt) or an ammonium salt (preferably quaternary ammonium salt).
- the divalent linking group represented by Y is selected from —CO—, —O—, —NH—, a divalent aliphatic group, a divalent aromatic group, and combinations of these divalent groups. And a divalent linking group. Specific examples of the divalent linking group comprising the combination are given below. In the following specific examples, the left side is bonded to the main chain, and the right side is bonded to the hydrophilic group (W).
- the divalent aliphatic group examples include an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group, and a polyalkyleneoxy group.
- it is an alkylene group, a substituted alkylene group, an alkenylene group or a substituted alkenylene group, more preferably an alkylene group or a substituted alkylene group.
- the divalent aliphatic group preferably has a chain structure rather than a cyclic structure, and more preferably has a linear structure rather than a branched chain structure.
- the number of carbon atoms in the divalent aliphatic group is preferably 1-20, more preferably 1-15, still more preferably 1-12, still more preferably 1-10, and particularly preferably 1-8.
- Examples of the substituent of the divalent aliphatic group include a halogen atom (F, Cl, Br, I), a hydroxy group, a carboxyl group, an amino group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, and an acyl group. , Alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, monoalkylamino group, dialkylamino group, arylamino group and diarylamino group.
- a halogen atom F, Cl, Br, I
- Examples of the divalent aromatic group include an arylene group and a substituted arylene group. Preferable are phenylene, substituted phenylene group, naphthylene or substituted naphthylene group.
- Examples of the substituent for the divalent aromatic group include an alkyl group in addition to the examples of the substituent for the divalent aliphatic group.
- L1 to L19 L1, L3, L5, L7 or L17 is preferable.
- the support used for the lithographic printing plate precursor according to the invention is a substrate having a hydrophilic surface or a substrate having a hydrophilic surface provided by coating a hydrophilic layer or the like.
- paper, paper laminated with plastic for example, polyethylene, polypropylene, polystyrene, etc.
- metal plate for example, aluminum, zinc, copper, etc.
- plastic film for example, cellulose diacetate, cellulose triacetate, Cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.
- a coated substrate may be mentioned.
- a preferable support includes a polyester film coated with an aluminum plate and a hydrophilic layer.
- the aluminum plate includes a pure aluminum plate and an alloy plate containing aluminum as a main component and containing a trace amount of different elements, and may be a plate obtained by laminating plastic on a thin plate of aluminum or an aluminum alloy.
- Examples of foreign elements contained in the aluminum alloy include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, and titanium. The content of foreign elements in the alloy is 10% or less.
- an aluminum plate from an aluminum ingot using a DC casting method or an aluminum plate from an ingot by a continuous casting method may be used.
- conventionally publicly known materials such as JIS A 1050, JIS A 1100, JIS A 3103, JIS A 3005, and the like can be used as appropriate.
- the thickness of the substrate is usually 0.05 to 0.6 mm, preferably 0.1 to 0.4 mm, and particularly preferably 0.15 to 0.3 mm.
- an aluminum plate for a lithographic printing plate precursor includes a degreasing step for removing rolling oil adhering to the aluminum plate, a desmutting step for dissolving and removing the smut on the surface of the aluminum plate, and a roughening for roughening the surface of the aluminum plate. It is manufactured through the surface treatment process.
- the aluminum plate is subjected to a dissolution treatment using an alkaline aqueous solution such as caustic soda to remove strong dirt and natural oxide film, etc., and neutralizes residual alkali components after the treatment.
- neutralization treatment is performed by immersing in an acid such as nitric acid, sulfuric acid, hydrochloric acid, chromic acid or a mixed acid thereof.
- an acid such as nitric acid, sulfuric acid, hydrochloric acid, chromic acid or a mixed acid thereof.
- a solvent degreasing treatment with trichlene, thinner or the like, or an emulsion degreasing treatment with an emulsion such as kerosene or triethanol may be performed.
- the type and composition of the acid used for the neutralization treatment are changed to the electrochemical roughening treatment. It is preferable to match the type and composition of the acid used for the treatment.
- the roughening treatment of the aluminum plate surface is performed by various methods. Examples thereof include a method of mechanically roughening, a method of electrochemically dissolving and roughening a surface, a method of chemically selectively dissolving a surface, and a combination of these methods.
- the mechanical roughening method a known method such as a ball polishing method, a brush polishing method, a blast polishing method, or a buff polishing method can be used.
- the chemical roughening method a method of immersing in a saturated aqueous solution of an aluminum salt of a mineral acid as described in JP-A No. 54-31187 is suitable.
- an electrochemical surface roughening method there is a method of performing alternating current or direct current in an electrolytic solution containing an acid such as hydrochloric acid or nitric acid.
- an electrolytic chemical roughening method using a mixed acid can also be used.
- the roughening is preferably performed in such a range that the center line average roughness (Ra) of the aluminum plate surface is 0.2 to 1.0 ⁇ m.
- the roughened aluminum plate is subjected to an alkali etching treatment using an aqueous solution such as potassium hydroxide or sodium hydroxide as necessary, and further subjected to a neutralization treatment.
- an alkali etching treatment using an aqueous solution such as potassium hydroxide or sodium hydroxide as necessary, and further subjected to a neutralization treatment.
- a hydrophilic film on the aluminum plate that has been subjected to the surface roughening treatment and other treatments as necessary.
- a support provided with a hydrophilic film having a density of 1000 to 3200 kg / m 3 has good film strength and resistance to stains in printing, and heat generated in the image recording layer is dissipated to the support. It is preferable because of its good heat insulating property.
- the density is measured by, for example, observing the mass and cross section of the hydrophilic layer with a Mason method (dissolving the hydrophilic film with a chromic acid / phosphoric acid mixed solution to obtain the mass of the hydrophilic film) with a scanning electron microscope (SEM). It can calculate with the following formula
- Density (kg / m 3 ) (hydrophilic film mass per unit area) / film thickness
- the hydrophilic film density is less than 1000 kg / m 3 , the film strength is low, which may adversely affect image forming properties, printing durability, and the like, and may be less resistant to smearing during printing. If the hydrophilic film density exceeds 3200 kg / m 3 , sufficient heat insulation cannot be obtained, and the sensitivity improvement effect may be reduced.
- the method for providing the hydrophilic film is not particularly limited, and an anodizing method, a vapor deposition method, a CVD method, a sol-gel method, a sputtering method, an ion plating method, a diffusion method, and the like can be appropriately used. Moreover, the method of apply
- an anodizing process that is, an anodizing process.
- the anodizing treatment can be performed by a method conventionally used in this field. Specifically, when direct current or alternating current is applied to an aluminum plate in an aqueous solution or non-aqueous solution of sulfuric acid, phosphoric acid, chromic acid, oxalic acid, sulfamic acid, benzenesulfonic acid, etc., alone or in combination of two or more.
- An anodized film that is a hydrophilic film can be formed on the surface of the aluminum plate.
- the conditions for anodizing treatment vary depending on the electrolyte used, and cannot be determined unconditionally. In general, however, the electrolyte concentration is 1 to 80%, the solution temperature is 5 to 70 ° C., and the current density is 0.5 to 60 A / dm 2 , voltage 1 to 200 V, and electrolysis time 1 to 1000 seconds are suitable.
- anodizing treatments a method of anodizing at a high current density in a sulfuric acid electrolyte solution described in British Patent No. 1,412,768, an anode using phosphoric acid described in US Pat. No. 3,511,661 as an electrolytic bath A method of oxidation treatment is preferred. Further, multi-stage anodizing treatment such as anodizing treatment in sulfuric acid and further anodizing treatment in phosphoric acid can be performed.
- the amount of the anodized film is preferably 1.5 g / m 2 or more from the viewpoint of effectively preventing the non-image area from being damaged and causing stains.
- the support may be a substrate having the roughened surface as described above and having an anodized film as it is, but for further improvement of adhesiveness with the upper layer, hydrophilicity, dirt resistance, heat insulation, etc., as necessary.
- Surface pores immersed in an aqueous solution containing a hydrophilic compound, and micropore enlargement treatment, micropore sealing treatment of the anodized film described in JP-A Nos. 2001-253181 and 2001-322365 It is possible to appropriately select and perform the conversion process.
- Suitable hydrophilic compounds for surface hydrophilization treatment include polyvinylphosphonic acid, compounds having sulfonic acid groups, saccharide compounds, citric acid, alkali metal silicates, potassium zirconium fluoride, phosphate / inorganic fluorine compounds, etc. Can be mentioned.
- the lithographic printing plate precursor according to the present invention has a hydrophilic property on the image recording layer in order to protect the hydrophilic image recording layer surface from contamination with lipophilic substances during storage and fingerprint trace contamination due to finger contact during handling.
- An overcoat layer can be provided.
- the overcoat layer can be easily removed on a printing press, and contains a water-soluble resin or a water-swellable resin partially crosslinked with a water-soluble resin.
- the water-soluble resin is selected from water-soluble natural polymers and synthetic polymers, and the film after coating and drying has a film-forming ability when used alone or in combination with a crosslinking agent.
- water-soluble resins preferably used include natural gums, gum arabic, water-soluble soybean polysaccharide, fiber derivatives (eg, carboxymethylcellulose, carboxyethylcellulose, methylcellulose, etc.), modified products thereof, white dextrin, pullulan.
- Synthetic polymers such as enzymatically decomposed etherified dextrin, polyvinyl alcohol (polyvinyl acetate having a hydrolysis degree of 65% or more), polyacrylic acid, alkali metal salt or amine salt thereof, polyacrylic acid copolymer, Alkali metal salt or amine salt, polymethacrylic acid, alkali metal salt or amine salt thereof, vinyl alcohol / acrylic acid copolymer, alkali metal salt or amine salt thereof, polyacrylamide, copolymer thereof, polyhydroxyethyl acrylate, polyvinyl Pylori , Copolymers thereof, polyvinyl methyl ether, vinyl methyl ether / maleic anhydride copolymer, poly-2-acrylamido-2-methyl-1-propanesulfonic acid, alkali metal salts or amine salts thereof, poly-2- Mention may be made of acrylamido-2-methyl-1-propanesulfonic acid copolymer, its alkali metal salt
- the crosslinking is performed by a crosslinking reaction using a reactive functional group of the water-soluble resin.
- the crosslinking reaction may be a covalent bond or an ionic bond.
- Crosslinking reduces the adhesiveness of the surface of the overcoat layer and improves the handleability of the lithographic printing plate precursor, but if the crosslinking proceeds too much, the overcoat layer changes to oleophilic, and the overcoat layer on the printing press Since removal becomes difficult, moderate partial cross-linking is preferred.
- the preferred degree of partial cross-linking is that when the lithographic printing plate precursor is immersed in water at 25 ° C., the overcoat layer does not dissolve for 30 seconds to 10 minutes, but elution is observed after 10 minutes or more. It is.
- Examples of the compound (crosslinking agent) used in the crosslinking reaction include known polyfunctional compounds having crosslinkability. Specifically, polyepoxy compounds, polyamine compounds, polyisocyanate compounds, polyalkoxysilyl compounds, titanates. Examples thereof include compounds, aldehyde compounds, polyvalent metal salt compounds, hydrazine and the like.
- the crosslinking agent can be used alone or in combination of two or more.
- a particularly preferred crosslinking agent is a water-soluble crosslinking agent, but a water-insoluble crosslinking agent can be used by dispersing in water with a dispersant.
- Preferred combinations of water-soluble resins and crosslinking agents include carboxylic acid-containing water-soluble resins / polyvalent metal compounds, carboxylic acid-containing water-soluble resins / water-soluble epoxy resins, and hydroxyl group-containing resins / dialdehydes.
- a suitable addition amount of the crosslinking agent is 2 to 10% by mass of the water-soluble resin. Within this range, it is possible to prevent contamination of the image recording layer with an oleophilic substance without impairing the removability of the overcoat layer on the printing press.
- the overcoat layer can contain a water-soluble infrared absorber to improve sensitivity.
- the infrared absorbing dye used for the image recording layer is preferably used.
- a nonionic surfactant can be mainly added to the overcoat layer for the purpose of ensuring uniformity of coating.
- the nonionic surfactant include sorbitan tristearate, sorbitan monopalmitate, sorbitan trioleate, stearic acid monoglyceride, polyoxyethylene nonylphenyl ether, polyoxyethylene dodecyl ether and the like.
- the addition amount of the nonionic surfactant is preferably 0.05 to 5%, more preferably 1 to 3% in the solid matter of the overcoat layer.
- the thickness of the overcoat layer is preferably 0.1 to 4.0 ⁇ m, more preferably 0.1 to 1.0 ⁇ m when the water-soluble resin is not crosslinked, and the water-soluble resin is partially crosslinked. In the case, it is preferably 0.1 to 0.5 ⁇ m, more preferably 0.1 to 0.3 ⁇ m. Within this range, it is possible to prevent the image recording layer from being contaminated by an oleophilic substance without impairing the removability of the overcoat layer on the printing press.
- the plate making method of the lithographic printing plate precursor according to the invention includes a step of image exposing the lithographic printing plate precursor and a step of developing the exposed lithographic printing plate precursor on the machine.
- Image exposure is performed by, for example, scanning exposure using an infrared laser, infrared lamp exposure, or the like, and exposure using a solid high-power infrared laser such as a semiconductor laser emitting a wavelength of 700 to 1200 nm or a YAG laser is preferable.
- the lithographic printing plate precursor according to the invention is preferably exposed using a laser, a pulse laser, a solid laser, or a semiconductor laser. Exposure of this case, the surface exposure intensity before modulation by printing image is preferably 0.1 ⁇ 10J / cm 2, more preferably 0.1 ⁇ 1J / cm 2.
- the image-exposed lithographic printing plate precursor is mounted on the impression cylinder of the printing press without further processing, and then developed on-press by a normal printing start operation for supplying dampening water and ink, followed by printing. be able to.
- the lithographic printing plate precursor is mounted on the plate cylinder of the printing press, then exposed by the exposure device of the printing press, and subsequently developed on the press for printing. it can.
- a plate making method in which the lithographic printing plate precursor is image-exposed with an infrared laser and then the unexposed portion of the image recording layer is removed on the printing machine using at least one of printing ink and fountain solution is preferable.
- the molecular weight is a mass average molar mass (Mw), and the ratio of repeating units is a mole percentage, except for those specifically defined.
- SM-001 (199.5 g) was dissolved in methanol (1.8 l) and a solution of KOH (41.6 g) in water (120 ml) was added over 30 minutes with vigorous stirring. After stirring at room temperature for 1 hour, the reaction mixture was cooled to 15 ° C. The formed precipitate was collected by filtration, washed twice with cold ethanol (100 ml) on the filter, and air-dried to obtain SM-002 (177.2 g).
- a comparative infrared absorbing dye IR-C was synthesized according to the following scheme.
- An aluminum plate having a thickness of 0.19 mm was degreased by immersing it in a 40 g / l sodium hydroxide aqueous solution at 60 ° C. for 8 seconds and washed with demineralized water for 2 seconds.
- the aluminum plate is then placed in an aqueous solution containing 12 g / l hydrochloric acid and 38 g / l aluminum sulfate (18 hydrate) using an alternating current for 15 seconds at a temperature of 33 ° C. and a current density of 130 A / dm 2.
- An electrochemical roughening treatment was performed.
- the aluminum plate was desmutted by etching with 155 g / l sulfuric acid aqueous solution at 70 ° C. for 4 seconds, and washed with demineralized water at 25 ° C. for 2 seconds.
- the aluminum plate was anodized in a 155 g / l sulfuric acid aqueous solution for 13 seconds at a temperature of 45 ° C. and a current density of 22 A / dm 2 and washed with demineralized water for 2 seconds. Further, it was post-treated with a 4 g / l aqueous polyvinylphosphonic acid solution at 40 ° C. for 10 seconds, washed with desalted water at 20 ° C. for 2 seconds, and dried.
- the support thus obtained had a surface roughness Ra of 0.21 ⁇ m and an anodized film amount of 4 g / m 2 .
- intermediate layer coating solutions A to C having the following compositions were prepared.
- the intermediate layer coating solution was applied onto the support and dried at 100 ° C. for 60 seconds to form an intermediate layer.
- the coating amount after drying of the intermediate layer polymer is shown in Table 1.
- Intermediate layer coating solution A (Intermediate layer coating solution A) ⁇ Intermediate layer polymer A 0.017 g ⁇ 8g of n-propanol ⁇ Water 2g
- thermoplastic fine particle polymer, infrared absorbing dye, and polyglycerol compound shown in Table 1 below was prepared, and after adjusting the pH to 3.6, on the above support or intermediate layer And dried at 50 ° C. for 1 minute to form an image recording layer to prepare a lithographic printing plate precursor.
- Table 1 shows the coating amount of the image recording layer components after drying.
- thermoplastic fine particle polymer polyglycerol compounds PG-1 to PG-3, comparative compounds X to Z, other components PAA and PVA, surfactant, infrared absorbing dye IR-C used in the image recording layer coating liquid are as follows. As shown in The infrared absorbing dyes IR-1 and IR-5 and the comparative infrared absorbing dye IR-C are the infrared absorbing dyes described above.
- Thermoplastic particulate polymer styrene / acrylonitrile copolymer (molar ratio 50/50), Tg: 99 ° C., average particle size: 61 nm
- Polyglycerol compound PG-1 Polyglycerin PGL 10 (number of repeating units: 10) (manufactured by Daicel Corporation)
- Polyglycerol compound PG-2 Polyglycerol PGL 6 (number of repeating units: 6) (manufactured by Daicel Corporation)
- Polyglycerol compound PG-3 Polyglycerin PGL X (number of repeating units: 40) (manufactured by Daicel Corporation)
- Compound Y for comparison decaglycerin oleate (trade name Poem J-0381V manufactured by Riken Vitamin Co., Ltd
- thermocondition A and thermocondition B were evaluated for visibility, on-press developability and printing durability as follows. The evaluation was performed using a lithographic printing plate precursor immediately after preparation and a lithographic printing plate precursor subjected to forced aging according to the following thermocondition A and thermocondition B. Further, the background stain (stain on the non-image area) was evaluated using a lithographic printing plate precursor forcibly aged according to the following thermo condition A and thermo condition B.
- the prepared lithographic printing plate precursor and slip sheet (the slip sheet described in Example 1 of JP-A-2003-302749 (corresponding to EP1, 353, 221B1)) are alternately stacked, and 50 lithographic printing plate precursors are used as one case. Packed. The packed lithographic printing plate precursor was stored in an environment of 50 ° C. and 50% RH for 1 day.
- lithographic printing plate precursor and slip sheet (the slip sheet described in Example 1 of JP-A-2003-302749 (corresponding to EP1, 353, 221B1)) are alternately stacked, and 50 lithographic printing plate precursors are used as one case. Packed. The packed lithographic printing plate precursor was stored in an environment of 50 ° C. and 60% RH for 2 days.
- the lithographic printing plate precursor was exposed with a Luxel PLANETSETTER T-6000III equipped with an infrared semiconductor laser under the conditions of an outer drum rotation speed of 1000 rpm, a laser output of 70%, and a resolution of 2400 dpi.
- the exposure image included a solid image and a 50% halftone dot chart of a 20 ⁇ m dot FM screen.
- CM-2500d manufactured by Konica Minolta
- L * a * b * is measured at a viewing angle of 10 ° and a light source D65 for each of the solid exposed portion and the unexposed portion of the image recording layer. I did it.
- ⁇ L * is 7 or more and less than 10 3: ⁇ L * is 5 or more and less than 7 2: ⁇ L * is 3 or more and less than 5 1: ⁇ L * is greater than 0 to 3 Is less than
- Print life Printing was further continued after the on-press developability evaluation. As the number of printed sheets was increased, the image recording layer was gradually worn out, so that the ink density on the printed material decreased. The number of copies printed when the dot area ratio of 50% halftone dots of FM screen in the printed matter was 5% lower than the measurement value of the 100th printed sheet was evaluated as printing durability. The results are shown in Table 2.
- thermo-condition A Using the lithographic printing plate precursor forcibly aged according to the following thermo-condition A and thermo-condition B, printing is performed in the same manner as described above, and the density (background stain) of the non-image area is measured with a Gretag densitometer on the 500th printed material. did. The results are shown in Table 2. Note that the background stains measured in the same manner as described above using a planographic printing plate precursor before aging (immediately after preparation) were all less than 0.1.
- the image recording layer contains the infrared-absorbing dye and the polyglycerol compound according to the present invention, so that it is excellent in visibility and on-press developability even when stored for a long time.
- a heat fusion type lithographic printing plate precursor can be obtained (Examples 1 to 3).
- the printing durability is improved, and deterioration in on-press development and printing durability when stored for a long period of time is prevented ( Examples 4 to 10).
- the image recording layer does not contain a polyglycerol compound (Comparative Example 1)
- the on-press developability when stored for a long period of time is significantly deteriorated.
- a polyglycerin ester having a long-chain alkyl group such as decaglycerin monolaurate
- the on-press developability is deteriorated when stored for a long period of time.
- the image recording layer does not contain a polyglycerol compound and an intermediate layer containing a compound having a phosphoric acid group or a phosphonic acid group is provided (Comparative Example 2)
- the on-press developability when stored for a long period of time Will deteriorate significantly.
- a heat fusion type lithographic printing plate precursor having excellent visibility and excellent on-press developability even after long-term storage of the lithographic printing plate precursor can be obtained.
- a heat fusion type lithographic printing plate precursor having excellent storage stability can be obtained.
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Abstract
Description
従来、親水性の支持体上に親油性の感光性樹脂層(画像記録層、画像形成層)を有する平版印刷版原版(PS版)を用い、この平版印刷版原版にリスフィルムなどのマスクを通した画像露光を行った後、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。
平版印刷版原版から平版印刷版を作製する製版工程は、簡易化が進み、画像露光に関しては、現在、平版印刷版は、CTP(コンピュータ・トゥ・プレート)技術によって得られるようになっている。すなわち、レーザーやレーザーダイオードを用いて、リスフィルムを介することなく、平版印刷版原版を直接走査露光し、現像処理して平版印刷版が得られる。
機上現像型平版印刷版原版としては、赤外線吸収剤、重合開始剤、重合性化合物を含有する画像記録層を支持体上に有する平版印刷版原版(例えば、特許文献1)及び赤外線吸収剤、熱可塑性ポリマー粒子を含有する画像記録層を支持体上に有する平版印刷版原版(例えば、特許文献2)が知られている。
しかし、特定構造のIR染料を含む感熱性像形成要素は、経時により、その機上現像性が著しく低下することが認められる。即ち、特許文献3に記載の感熱性像形成要素は、視認性(検版性)に優れるものの保存後の機上現像性が劣るという問題がある。
従って、視認性及び経時後の機上現像性において優れた熱融着型の平版印刷版原版の提供が望まれている。
(1)支持体上に、(A)熱可塑性微粒子ポリマー、(B)赤外線吸収染料、及び(C)ポリグリセロール化合物を含有する画像記録層を有する平版印刷版原版であって、上記赤外線吸収染料が下記一般式(I)で表される赤外線吸収染料であり、上記ポリグリセロール化合物が下記一般式(1)及び一般式(2)で表される構造単位のいずれかを3つ以上有する化合物である平版印刷版原版。
-NR10-L-X-Y 一般式(Ia)
一般式(Ia)中、R10は、水素原子、脂肪族炭化水素基又は(ヘテロ)アリール基を表すか、或いは、Yと連結して環状構造を形成するのに必要な原子群を表す。Lは、単結合又は2価の連結基を表す。Xは、-CO-、-SO2-又は-SO-を表す。Yは、-R11a、-OR11b、-NR12R13又は-CF3を表す。R11aは、水素原子、脂肪族炭化水素基又は(ヘテロ)アリール基を表す。R11bは、脂肪族炭化水素基又は(ヘテロ)アリール基を表す。R12及びR13は、それぞれ独立に水素原子、脂肪族炭化水素基又は(ヘテロ)アリール基を表すか、或いは、R12及びR13が互いに連結して環状構造を形成するのに必要な原子群を表す。
(2)上記一般式(1)及び一般式(2)で表される構造単位におけるAが、水素原子である上記(1)に記載の平版印刷版原版。
(3)上記一般式(Ia)中、Xが-CO-である上記(1)又は(2)に記載の平版印刷版原版。
(4)上記一般式(Ia)中、Yが-OR11bであり、上記R11bがアルファー位分岐鎖状の脂肪族炭化水素基である上記(1)~(3)のいずれか一項に記載の平版印刷版原版。
(5)上記R11bが、3級ブチル基である上記(4)に記載の平版印刷版原版。
(6)上記支持体と上記画像記録層との間に、リン酸基又はホスホン酸基を有する化合物を含有する中間層を有する上記(1)~(5)のいずれか一項に記載の平版印刷版原版。
(7)上記リン酸基又はホスホン酸基を有する化合物が、高分子化合物である上記(6)に記載の平版印刷版原版。
(8)上記リン酸基又はホスホン酸基を有する化合物が、更に親水性基を有する化合物である上記(6)又は(7)に記載の平版印刷版原版。
(9)上記(1)~(8)のいずれか一項に記載の平版印刷版原版を、赤外線レーザーにより画像露光した後、印刷機上で印刷インキ及び湿し水の少なくともいずれかを用いて画像記録層未露光部分を除去する製版方法。
本発明の平版印刷版原版は、支持体上に、(A)熱可塑性微粒子ポリマー、(B)赤外線吸収染料、及び(C)ポリグリセロール化合物を含有する画像記録層を有する平版印刷版原版であって、上記赤外線吸収染料が下記一般式(I)で表される赤外線吸収染料であり、上記ポリグリセロール化合物が下記一般式(1)及び一般式(2)で表される構造単位のいずれかを3つ以上有する化合物であることを特徴とする。
-NR10-L-X-Y 一般式(Ia)
一般式(Ia)中、R10は、水素原子、脂肪族炭化水素基又は(ヘテロ)アリール基を表すか、或いは、Yと連結して環状構造を形成するのに必要な原子群を表す。Lは、単結合又は2価の連結基を表す。Xは、-CO-、-SO2-又は-SO-を表す。Yは、-R11a、-OR11b、-NR12R13又は-CF3を表す。R11aは、水素原子、脂肪族炭化水素基又は(ヘテロ)アリール基を表す。R11bは、脂肪族炭化水素基又は(ヘテロ)アリール基を表す。R12及びR13は、それぞれ独立に水素原子、脂肪族炭化水素基又は(ヘテロ)アリール基を表すか、或いは、R12及びR13が互いに連結して環状構造を形成するのに必要な原子群を表す。
本発明の平版印刷版原版は、画像露光後、印刷機上における機上現像により平版印刷版を作製することができる。
以下に、本発明の平版印刷版原版について詳細に説明する。
本発明の平版印刷版原版における画像記録層は、(A)熱可塑性微粒子ポリマー、(B)赤外線吸収染料、及び(C)ポリグリセロール化合物を含有する。画像記録層に含有される成分について、以下に説明する。
本発明の平版印刷版原版の画像記録層に含まれる熱可塑性微粒子ポリマーはそのガラス転移温度(Tg)が60℃~250℃であることが好ましい。熱可塑性微粒子ポリマーのTgは、70℃~140℃がより好ましく、80℃~120℃が更に好ましい。
Tgが60℃以上の熱可塑性微粒子ポリマーとしては、例えば、1992年1月のReseach Disclosure No.33303、特開平9-123387号公報、同9-131850号公報、同9-171249号公報、同9-171250号公報及びEP931647号公報などに記載の熱可塑性微粒子ポリマーを好適なものとして挙げることができる。
具体的には、エチレン、スチレン、塩化ビニル、アクリル酸メチル、アクリル酸エチル、メタクリル酸メチル、メタクリル酸エチル、塩化ビニリデン、アクリロニトリル、ビニルカルバゾールなどのモノマーから構成されるホモポリマー若しくはコポリマー又はそれらの混合物などを例示することができる。好ましいものとして、ポリスチレン、ポリメタクリル酸メチルなどが挙げられる。
例えば、熱可塑性微粒子ポリマーとして粒子サイズが同じものを用いた場合には、熱可塑性微粒子ポリマー間にある程度の空隙が存在することになり、画像露光により熱可塑性微粒子ポリマーを溶融固化させても皮膜の硬化性が所望のものにならないことがある。これに対して、熱可塑性微粒子ポリマーとして粒子サイズが異なるものを用いた場合、熱可塑性微粒子ポリマー間にある空隙率を低くすることができ、その結果、画像露光後の画像部の皮膜硬化性を向上させることができる。
架橋性基の導入を微粒子ポリマーの重合後に行う場合に用いる高分子反応としては、例えば、WO96/34316号に記載されている高分子反応を挙げることができる。
熱可塑性微粒子ポリマーは、架橋性基を介して微粒子ポリマー同士が反応してもよいし、画像記録層に添加された高分子化合物あるいは低分子化合物と反応してもよい。
本発明の平版印刷版原版の画像記録層に含まれる赤外線吸収染料は、下記一般式(I)で表される赤外線吸収染料である。
-NR10-L-X-Y 一般式(Ia)
一般式(Ia)中、R10は、水素原子、脂肪族炭化水素基又は(ヘテロ)アリール基を表すか、或いは、Yと連結して環状構造を形成するのに必要な原子群を表す。Lは、単結合又は2価の連結基を表す。Xは、-CO-、-SO2-又は-SO-を表す。Yは、-R11a、-OR11b、-NR12R13又は-CF3を表す。R11aは、水素原子、脂肪族炭化水素基又は(ヘテロ)アリール基を表す。R11bは、脂肪族炭化水素基又は(ヘテロ)アリール基を表す。R12及びR13は、それぞれ独立に水素原子、脂肪族炭化水素基又は(ヘテロ)アリール基を表すか、或いは、R12及びR13が互いに連結して環状構造を形成するのに必要な原子群を表す。
ここで、「(ヘテロ)アリール基」の用語は、アリール基及びヘテロアリール基の総称として用いる。
Ar1又はAr2で表されるベンゼン環又はナフタレン環は置換基を有していてもよく、置換基の例としては、炭素原子数12以下のアルキル基、ハロゲン原子、炭素原子数12以下のアルコキシ基などが挙げられる。
R4又はR5で表されるアルキル基は炭素原子数20以下のアルキル基が好ましい。アルキル基は置換基を有していてもよく、置換基の例としては、炭素原子数12以下のアルコキシ基、カルボキシル基、スルホ基などが挙げられる。
R6、R7、R8又はR9で表されるアルキル基は炭素原子数12以下のアルキル基が好ましい。
Zaで表される電荷を中和する対アニオンは、好ましくはハロゲン化物イオン、過塩素酸イオン、テトラフルオロボレートイオン、ヘキサフルオロホスフェートイオン又はスルホン酸イオンであり、より好ましくは、過塩素酸イオン、ヘキサフルオロホスフェートイオン又はアリールスルホン酸イオンである。なお、一般式(I)で表される赤外線吸収染料がその構造内にアニオン性の置換基を有し電荷の中和が必要ない場合にはZaは必要ない。
R11a又はR11bで表されるヘテロアリール基は、ヘテロ原子として、酸素原子、窒素原子、硫黄原子、セレン原子のいずれかを含むことが好ましい。ヘテロ原子は酸素原子、窒素原子、硫黄原子であることがより好ましく、酸素原子、窒素原子であることが特に好ましい。ヘテロアリール基は置換基を有していてもよく、置換基の例としては、上記アリール基が有してもよい置換基として例示したものが挙げられる。
Lは、視認性向上の観点からは、単結合又はアルキレン基、-CO-、-O-、-NH-から選ばれる2以上の組み合わせからなる2価の連結基が好ましく、単結合又は炭素数8以下のアルキレン基、-CO-、-O-、-NH-から選ばれる2以上の組み合わせからなる2価の連結基がより好ましい。
また、視認性向上の観点からは、Yが-OR11bであることが好ましく、ここで、R11bは好ましくはアルファー位分岐鎖状の脂肪族炭化水素基、より好ましくは第二級又は第三級脂肪族炭化水素基、特に好ましくは第三級ブチル基である。
本発明に係る平版印刷版原版の画像記録層に含まれるポリグリセロール化合物は、下記一般式(1)及び一般式(2)で表される構造単位のいずれかを3つ以上有する化合物である。
また、市販品も利用でき、例えば、ポリグリセリン #310、ポリグリセリン #500、ポリグリセリン #750(以上、坂本薬品工業(株)製)、ポリグリセリン(四日市合成(株)製)、ポリグリセリン PGL 06、ポリグリセリン PGL 10、ポリグリセリン PGL X(以上、(株)ダイセル製)などが挙げられる。
これに対して、ポリグリセロール化合物を併用することにより、経時による機上現像性の悪化を抑制することができる。これは、ポリグリセロール化合物が多数のヒドロキシ基を有しており、ヒドロキシ基の一部が炭素数4以下のアルキル基又は炭素数5以下のアルキルカルボニル基で置換されている場合でも、ポリグリセロール化合物の親水性は極めて高く、機上現像の際に湿し水の浸透パスとして機能するためと考えられる。
また、ポリグリセロール化合物は、親水性が高く、界面活性作用を実質的に示さない。このため、機上現像時において、湿し水が画像記録層の露光部(画像部)へ浸透して画像部の疎水性や皮膜強度を低下させることがなく、画像部のインキ受容性や耐刷性を良好に維持することが可能となる。
無機微粒子の含有量は、画像記録層固形分の1.0~70質量%が好ましく、5.0~50質量%がより好ましい。
アニオン界面活性剤は、上記目的を達成する限り、特に制限されない。中でも、アルキルベンゼンスルホン酸又はその塩、アルキルナフタレンスルホン酸又はその塩、(ジ)アルキルジフェニルエーテル(ジ)スルホン酸又はその塩、アルキル硫酸エステル塩が好ましい。
アニオン界面活性剤の添加量は、画像記録層固形分の0.1~30質量%が好ましく、0.1~20質量%がより好ましく、画像記録層の強度と非画像部の現像性を両立する観点からは、0.1~10質量%が特に好ましい。
本発明の画像記録層は、必要な上記各成分を適当な溶剤に溶解又は分散して塗布液を調製し、支持体に塗布して形成される。溶剤としては、水又は水と有機溶剤との混合溶剤が用いられるが、水と有機溶剤の混合使用が、塗布後の面状を良好にする点で好ましい。有機溶剤の量は、有機溶剤の種類によって異なるので、一概に特定できないが、通常混合溶剤中5~50容量%が好ましい。但し、有機溶剤は熱可塑性微粒子ポリマーが凝集しない範囲の量で使用する必要がある。画像記録層用塗布液の固形分濃度は、好ましくは1~50質量%である。
リン酸基又はホスホン酸基を有する化合物としては、例えば、燐酸、ホスホン酸、燐酸エステル、アルキルホスホン酸及びこれらの塩をあげることができる。
L1:-CO-NH-二価の脂肪族基-O-CO-
L2:-CO-二価の脂肪族基-O-CO-
L3:-CO-O-二価の脂肪族基-O-CO-
L4:-二価の脂肪族基-O-CO-
L5:-CO-NH-二価の芳香族基-O-CO-
L6:-CO-二価の芳香族基-O-CO-
L7:-二価の芳香族基-O-CO-
L8:-CO-二価の脂肪族基-CO-O-二価の脂肪族基-O-CO-
L9:-CO-二価の脂肪族基-O-CO-二価の脂肪族基-O-CO-
L10:-CO-二価の芳香族基-CO-O-二価の脂肪族基-O-CO-
L11:-CO-二価の芳香族基-O-CO-二価の脂肪族基-O-CO-
L12:-CO-二価の脂肪族基-CO-O-二価の芳香族基-O-CO-
L13:-CO-二価の脂肪族基-O-CO-二価の芳香族基-O-CO-
L14:-CO-二価の芳香族基-CO-O-二価の芳香族基-O-CO-
L15:-CO-二価の芳香族基-O-CO-二価の芳香族基-O-CO-
L16:-CO-O-二価の芳香族基-O-CO-NH-二価の脂肪族基-O-CO-
L17:-CO-O-二価の脂肪族基-O-CO-NH-二価の脂肪族基-O-CO-
L18:-CO-NH-
L19:-CO-O-
二価の脂肪族基は、環状構造よりも鎖状構造の方が好ましく、更に分岐を有する鎖状構造より直鎖状構造が好ましい。二価の脂肪族基の炭素原子数は、1~20が好ましく、1~15がより好ましく、1~12が更に好ましく、1~10がより更に好ましく、1~8が特に好ましい。
二価の芳香族基の置換基の例としては、上記二価の脂肪族基の置換基の例に加えて、アルキル基が挙げられる。
本発明の平版印刷版原版に用いる支持体は、親水性表面を有する基板又は親水層の塗布などによって親水性表面を付与された基板である。具体的には、紙、プラスチック(例えば、ポリエチレン、ポリプロピレン、ポリスチレン等)がラミネートされた紙、金属板(例えば、アルミニウム、亜鉛、銅等)、プラスチックフィルム(例えば、二酢酸セルロース、三酢酸セルロース、プロピオン酸セルロース、酪酸セルロース、酢酸酪酸セルロース、硝酸セルロース、ポリエチレンテレフタレート、ポリエチレン、ポリスチレン、ポリプロピレン、ポリカーボネート、ポリビニルアセタール等)、上記金属がラミネート又は蒸着された紙又はプラスチックフィルム、又はこれら基板に親水層を塗布された基板が挙げられる。好ましい支持体としては、アルミニウム板及び親水層を塗布されたポリエステルフィルムが挙げられる。
本発明の平版印刷版原版は、保存時の親油性物質による汚染や取り扱い時の手指の接触による指紋跡汚染等から親水性の画像記録層表面を保護するため、画像記録層上に親水性のオーバーコート層を設けることができる。
本発明の平版印刷版原版の製版方法について、以下に説明する。本発明の平版印刷版原版の製版は、平版印刷版原版を画像露光する工程と、露光後の平版印刷用原版を機上現像する工程を含む。
画像露光は、例えば、赤外線レーザーによる走査露光、赤外線ランプ露光などにより行われるが、波長700~1200nmの赤外線を放射する半導体レーザー、YAGレーザー等の固体高出力赤外線レーザーによる露光が好適である。
(合成例1:赤外線吸収染料IR-1の合成)
下記スキームに従って、赤外線吸収染料IR-1を合成した。
下記スキームに従って、赤外線吸収染料IR-5を合成した。
(中間層ポリマーAの合成)
n-プロパノールと水を体積比4:1で混合した溶媒を反応フラスコに入れ、窒素によりパージしながら70℃に加熱した。窒素によるパージは、合成中継続して行なった。別途、35gのメタクリロイルエチルジメチルスルホプロピルアンモニウムヒドロキシド、15gのポリ(エチレングリコール)メタクリレート及びモノマーに対して0.6モル相当のアゾビスイソブチロニトリルを、n-プロパノールと水を体積比4:1で混合した溶媒に溶解させて50重量%溶液とした。この溶液を滴下漏斗に移し、反応フラスコ中の溶媒にゆっくりと滴下した。滴下終了後、10時間攪拌した。過剰の溶媒を真空中で除去し、得られた生成物を精製してポリマーAを得た。
特開2007-118579号に記載の方法に従って、下記の中間層ポリマーBを合成した。
特開2007-118579号に記載の方法に従って、下記の中間層ポリマーCを合成した。
〔平版印刷版原版の作製〕
厚さ0.19mmのアルミニウム板を40g/lの水酸化ナトリウム水溶液中に60℃で8秒間浸漬することにより脱脂し、脱塩水により2秒間洗浄した。次に、アルミニウム板を15秒間交流を用いて12g/lの塩酸及び38g/lの硫酸アルミニウム(18水和物)を含有する水溶液中で、33℃の温度及び130A/dm2の電流密度で電気化学的粗面化処理を行った。脱塩水により2秒間洗浄した後、アルミニウム板を155g/lの硫酸水溶液により70℃で4秒間エッチングすることによりデスマット処理し、脱塩水により25℃で2秒間洗浄した。アルミニウム板を13秒間155g/lの硫酸水溶液中で、45℃の温度及び22A/dm2の電流密度で陽極酸化処理し、脱塩水で2秒間洗浄した。更に、4g/lのポリビニルホスホン酸水溶液を用いて40℃で10秒間後処理し、脱塩水により20℃で2秒間洗浄し、乾燥した。このようにして得られた支持体は、表面粗さRaが0.21μmで、陽極酸化皮膜量は4g/m2であった。
上記中間層ポリマーA~Cを用いて、以下の組成の中間層塗布液A~Cを作製した。中間層塗布液を上記支持体上に塗布し、100℃で60秒間乾燥して中間層を形成した。中間層ポリマーの乾燥後の塗布量を表1に示す。
・中間層ポリマーA 0.017g
・n-プロパノール 8g
・水 2g
・中間層ポリマーB 0.017g
・メタノール 9g
・水 1g
・中間層ポリマーC 0.017g
・メタノール 9g
・水 1g
下記表1に示す熱可塑性微粒子ポリマー、赤外線吸収染料、ポリグリセロール化合物などの成分を含有する画像記録層塗布液を調製し、pHを3.6に調整した後、上記支持体上又は中間層上に塗布し、50℃で1分間乾燥して画像記録層を形成し、平版印刷版原版を作製した。画像記録層成分の乾燥後の塗布量を表1に示す。
ポリグリセロール化合物PG-1:ポリグリセリン PGL 10(繰り返し単位数:10)((株)ダイセル社製)
ポリグリセロール化合物PG-2:ポリグリセリン PGL 6(繰り返し単位数:6)((株)ダイセル社製)
ポリグリセロール化合物PG-3:ポリグリセリン PGL X(繰り返し単位数:40)((株)ダイセル社製)
比較用化合物X:デカグリセリンモノラウレート(商品名 ポエム J-0021 理研ビタミン(株)製)
比較用化合物Y:デカグリセリン オレート(商品名 ポエム J-0381V 理研ビタミン(株)製)
比較用化合物Z:グリセリン モノカプリレート(商品名 ポエム M-100 理研ビタミン(株)製)
他の成分PAA:ポリアクリル酸(商品名 グラスコル E15 アライド コロイズ マニュファクチュアリング製)
他の成分PVA:ビニルアルコール/酢酸ビニル共重合体(商品名 エルコル WX48/20 エルコル製)
界面活性剤:フッ素系界面活性剤(商品名 ゾニール FSO 100 デュポン製)
各平版印刷版原版について、視認性、機上現像性及び耐刷性を以下のように評価した。評価は作製直後の平版印刷版原版並びに下記サーモ条件A及びサーモ条件Bに従って強制経時させた平版印刷版原版を用いて行った。また、下記サーモ条件A及びサーモ条件Bに従って強制経時させた平版印刷版原版を用いて地汚れ(非画像部の汚れ)を評価した。
作製した平版印刷版原版及び合紙(特開2003-302749号(EP1、353、221B1に対応)の実施例1に記載の合紙)を交互に重ね、平版印刷版原版50枚を1ケースとして梱包した。梱包した平版印刷版原版を50℃、50%RHの環境下、1日間保存した。
作製した平版印刷版原版及び合紙(特開2003-302749号(EP1、353、221B1に対応)の実施例1に記載の合紙)を交互に重ね、平版印刷版原版50枚を1ケースとして梱包した。梱包した平版印刷版原版を50℃、60%RHの環境下、2日間保存した。
平版印刷版原版を赤外線半導体レーザー搭載の富士フイルム(株)製Luxel PLATESETTER T-6000IIIにて、外面ドラム回転数1000rpm、レーザー出力70%、解像度2400dpiの条件で露光した。露光画像にはベタ画像及び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。
画像記録層のベタ露光部と未露光部のそれぞれについて、分光測色計CM-2500d(コニカミノルタ社製)を用い、視野角10°、光源D65にて、L*a*b*の測定を行なった。得られた画像記録層のベタ露光部と未露光部のそれぞれの測定値から、SCEモードのL*値の差分ΔL*を算出し、以下の基準に従って評価を行なった。4及び3が実用上許容できるレベルである。結果を表2に示す。
3:ΔL*が、5以上~7未満である
2:ΔL*が、3以上~5未満である
1:ΔL*が、0より大きく~3未満である
露光後の平版印刷版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)の湿し水とスペースカラー フュージョンG(N)インキ(DICグラフィックス(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、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機上現像が完了し、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2に示す。
上記機上現像性評価を行った後、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耐刷性として評価した。結果を表2に示す。
下記サーモ条件A及びサーモ条件Bに従って強制経時させた平版印刷版原版を用いて、上記と同様に印刷を行い、500枚目の印刷物において非画像部の濃度(地汚れ)をグレタグ濃度計で計測した。結果を表2に示す。なお、経時前(作製直後)の平版印刷版原版を用いて、上記と同様にして測定した地汚れは、いずれも0.1未満であった。
また、リン酸基又はホスホン酸基を有する化合物を含有する中間層を設けることにより、耐刷性が向上し、長期間保存した場合における機上現像性及び耐刷性の低下が防止される(実施例4~10)。
これに対して、画像記録層がポリグリセロール化合物を含有しない場合(比較例1)には長期間保存した場合における機上現像性が大幅に劣化する。また、デカグリセリンモノラウレートのような長鎖アルキル基を有するポリグリセリンエステルを含有する場合(比較例3、4、5)にも長期間保存した場合における機上現像性が劣化する。
更に、画像記録層がポリグリセロール化合物を含有せず、リン酸基又はホスホン酸基を有する化合物を含有する中間層を設けた場合(比較例2)には長期間保存した場合における機上現像性が大幅に劣化する。
更に、一般式(I)で表される赤外線吸収染料におけるR1が、一般式(Ia)で表される基以外の基である比較用赤外線吸収染料を用いた場合(比較例6)では、視認性が大幅に劣る。
以上のことから、熱融着型平版印刷版原版の画像記録層に特定の赤外線吸収染料と共にポリグリセロール化合物を含有させることが、熱融着型平版印刷版原版の機上現像性の向上に特異的に有効であることが理解される。
本出願は、2013年7月18日出願の日本特許出願(特願2013-149862)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 (9)
- 支持体上に、(A)熱可塑性微粒子ポリマー、(B)赤外線吸収染料、及び(C)ポリグリセロール化合物を含有する画像記録層を有する平版印刷版原版であって、上記赤外線吸収染料が下記一般式(I)で表される赤外線吸収染料であり、上記ポリグリセロール化合物が下記一般式(1)及び一般式(2)で表される構造単位のいずれかを3つ以上有する化合物である平版印刷版原版。
一般式(I)中、R1は下記一般式(Ia)で表される基を表す。R2及びR3は、それぞれ独立に水素原子又はアルキル基を表すか、或いは、R2及びR3が互いに連結して環状構造を形成するのに必要な原子群を表す。Ar1及びAr2は、それぞれ独立にベンゼン環又はナフタレン環を形成するために必要な原子群を表す。Y1及びY2は、それぞれ独立に硫黄原子又はジアルキルメチレン基を表す。R4及びR5は、それぞれ独立にアルキル基を表す。R6、R7、R8及びR9は、それぞれ独立に水素原子又はアルキル基を表す。Zaは電荷を中和する対イオンを表す。
-NR10-L-X-Y 一般式(Ia)
一般式(Ia)中、R10は、水素原子、脂肪族炭化水素基又は(ヘテロ)アリール基を表すか、或いは、Yと連結して環状構造を形成するのに必要な原子群を表す。Lは、単結合又は2価の連結基を表す。Xは、-CO-、-SO2-又は-SO-を表す。Yは、-R11a、-OR11b、-NR12R13又は-CF3を表す。R11aは、水素原子、脂肪族炭化水素基又は(ヘテロ)アリール基を表す。R11bは、脂肪族炭化水素基又は(ヘテロ)アリール基を表す。R12及びR13は、それぞれ独立に水素原子、脂肪族炭化水素基又は(ヘテロ)アリール基を表すか、或いは、R12及びR13が互いに連結して環状構造を形成するのに必要な原子群を表す。
一般式(1)及び一般式(2)において、Aは水素原子、炭素原子数1~4のアルキル基又は炭素原子数2~5のアルキルカルボニル基を表す。 - 上記一般式(1)及び一般式(2)で表される構造単位におけるAが、水素原子である請求項1に記載の平版印刷版原版。
- 上記一般式(Ia)中、Xが-CO-である請求項1又は2に記載の平版印刷版原版。
- 上記一般式(Ia)中、Yが-OR11bであり、上記R11bがアルファー位分岐鎖状の脂肪族炭化水素基である請求項1~3のいずれか一項に記載の平版印刷版原版。
- 上記R11bが、3級ブチル基である請求項4に記載の平版印刷版原版。
- 上記支持体と上記画像記録層との間に、リン酸基又はホスホン酸基を有する化合物を含有する中間層を有する請求項1~5のいずれか一項に記載の平版印刷版原版。
- 上記リン酸基又はホスホン酸基を有する化合物が、高分子化合物である請求項6に記載の平版印刷版原版。
- 上記リン酸基又はホスホン酸基を有する化合物が、更に親水性基を有する化合物である請求項6又は7に記載の平版印刷版原版。
- 請求項1~8のいずれか一項に記載の平版印刷版原版を、赤外線レーザーにより画像露光した後、印刷機上で印刷インキ及び湿し水の少なくともいずれかを用いて画像記録層未露光部分を除去する製版方法。
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WO2018043259A1 (ja) * | 2016-08-31 | 2018-03-08 | 富士フイルム株式会社 | 発色組成物、平版印刷版原版、平版印刷版の作製方法、及び、化合物 |
WO2019004471A1 (ja) * | 2017-06-30 | 2019-01-03 | 富士フイルム株式会社 | 平版印刷版原版、及び平版印刷版の作製方法 |
US11370862B2 (en) * | 2016-11-16 | 2022-06-28 | Fujifilm Corporation | Radiation-sensitive composition, planographic printing plate precursor, and plate-making method for planographic printing plate |
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- 2014-06-20 WO PCT/JP2014/066440 patent/WO2015008578A1/ja active Application Filing
- 2014-06-20 JP JP2015527229A patent/JP6012870B2/ja not_active Expired - Fee Related
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WO2018043259A1 (ja) * | 2016-08-31 | 2018-03-08 | 富士フイルム株式会社 | 発色組成物、平版印刷版原版、平版印刷版の作製方法、及び、化合物 |
US11117364B2 (en) | 2016-08-31 | 2021-09-14 | Fujifilm Corporation | Color developing composition, lithographic printing plate precursor, method for producing lithographic printing plate, and compound |
US11370862B2 (en) * | 2016-11-16 | 2022-06-28 | Fujifilm Corporation | Radiation-sensitive composition, planographic printing plate precursor, and plate-making method for planographic printing plate |
WO2019004471A1 (ja) * | 2017-06-30 | 2019-01-03 | 富士フイルム株式会社 | 平版印刷版原版、及び平版印刷版の作製方法 |
CN110809521A (zh) * | 2017-06-30 | 2020-02-18 | 富士胶片株式会社 | 平版印刷版原版及平版印刷版的制作方法 |
JPWO2019004471A1 (ja) * | 2017-06-30 | 2020-03-19 | 富士フイルム株式会社 | 平版印刷版原版、及び平版印刷版の作製方法 |
CN110809521B (zh) * | 2017-06-30 | 2022-01-07 | 富士胶片株式会社 | 平版印刷版原版及平版印刷版的制作方法 |
US11543750B2 (en) | 2017-06-30 | 2023-01-03 | Fujifilm Corporation | Lithographic printing plate precursor and method for producing lithographic printing plate |
Also Published As
Publication number | Publication date |
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JP6012870B2 (ja) | 2016-10-25 |
JPWO2015008578A1 (ja) | 2017-03-02 |
US20160121596A1 (en) | 2016-05-05 |
DE112014003294T5 (de) | 2016-04-21 |
CN105408122A (zh) | 2016-03-16 |
CN105408122B (zh) | 2018-07-03 |
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