WO2018159640A1 - 硬化性組成物、平版印刷版原版、平版印刷版の作製方法、及び、化合物 - Google Patents
硬化性組成物、平版印刷版原版、平版印刷版の作製方法、及び、化合物 Download PDFInfo
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- WO2018159640A1 WO2018159640A1 PCT/JP2018/007359 JP2018007359W WO2018159640A1 WO 2018159640 A1 WO2018159640 A1 WO 2018159640A1 JP 2018007359 W JP2018007359 W JP 2018007359W WO 2018159640 A1 WO2018159640 A1 WO 2018159640A1
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- Prior art keywords
- group
- printing plate
- lithographic printing
- compound
- curable composition
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- 0 *c1ccc(*)cc1 Chemical compound *c1ccc(*)cc1 0.000 description 1
- MEVDNLQHIARCBU-UHFFFAOYSA-N CCC(C)(C)C(NCCCOCCOCCOCCCN)=O Chemical compound CCC(C)(C)C(NCCCOCCOCCOCCCN)=O MEVDNLQHIARCBU-UHFFFAOYSA-N 0.000 description 1
- IMGSYGPAZBTXKJ-UHFFFAOYSA-N CCC(C)(C)C(NCCCOCCOCCOCCCNC(C(C)=C)=O)=O Chemical compound CCC(C)(C)C(NCCCOCCOCCOCCCNC(C(C)=C)=O)=O IMGSYGPAZBTXKJ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C1/00—Forme preparation
- B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
- B41C1/1008—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
- B41N1/00—Printing plates or foils; Materials therefor
- B41N1/12—Printing plates or foils; Materials therefor non-metallic other than stone, e.g. printing plates or foils comprising inorganic materials in an organic matrix
- B41N1/14—Lithographic printing foils
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C311/48—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups having nitrogen atoms of sulfonamide groups further bound to another hetero atom
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
- C07D285/01—Five-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- 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
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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
- B41C2210/06—Developable by an alkaline 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
- B41C2210/08—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
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
- G03F7/2004—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light
- G03F7/2006—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light using coherent light; using polarised light
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/30—Imagewise removal using liquid means
- G03F7/32—Liquid compositions therefor, e.g. developers
- G03F7/325—Non-aqueous compositions
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/30—Imagewise removal using liquid means
- G03F7/32—Liquid compositions therefor, e.g. developers
- G03F7/325—Non-aqueous compositions
- G03F7/327—Non-aqueous alkaline compositions, e.g. anhydrous quaternary ammonium salts
Definitions
- the present invention relates to a curable composition, a lithographic printing plate precursor, a method of preparing a lithographic printing plate, and a compound.
- a curable composition in particular, a photocurable composition is a composition having a property of curing an irradiated part by irradiation of light, and a coating liquid formed by appropriately dissolving or dispersing this composition in a solvent is used.
- the photocurable film can be formed by coating on a suitable support and drying to form an image forming material.
- the image forming material include an image forming material utilizing curing by image exposure such as a lithographic printing plate precursor, a printed wiring board, a color filter, a photomask and the like.
- a lithographic printing plate precursor will be described as an example.
- 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.
- the lipophilic image area of the lithographic printing plate is an ink receiving area
- the hydrophilic non-image area is a dampening water receiving area (ink non-receiving area)
- the difference in the adhesion of the ink is produced on the surface of the lithographic printing plate, the ink is deposited only in the image area, and then the ink is transferred to a printing material such as paper for printing.
- image exposure is currently performed by the CTP (computer-to-plate) technique. That is, the image exposure is performed by scanning exposure etc. directly on the lithographic printing plate precursor using a laser or a laser diode without the lith film.
- CTP computer-to-plate
- On-machine development is a method in which the lithographic printing plate precursor is subjected to image exposure and then is not subjected to conventional development processing, and is attached as it is to a printing machine to remove non-image areas of the image recording layer at an early stage of ordinary printing process. .
- the lithographic printing plate precursor usually has an image recording layer on a support such as an aluminum plate.
- the image recording layer has a function of curing the exposed portion by image exposure to form an image portion. Therefore, the image recording layer contains components for forming an image by image exposure.
- produces a radical by exposure is mentioned.
- a salt compound composed of onium such as iodonium and sulfonium and inorganic or organic anion as a counter anion is used as the photopolymerization initiator contained in the image recording layer.
- Patent Document 1 describes a radiation-sensitive composition containing, as a photopolymerization initiator, a salt compound composed of a diaryliodonium cation of a specific structure and a borate anion of a specific structure.
- an operation to inspect or identify the image on the lithographic printing plate is performed whether the lithographic printing plate is intended for image recording.
- plate inspection it is important in the printing operation whether registration marks (register marks) serving as registration marks can be determined.
- a colored image can be obtained by development processing by coloring the image recording layer, so that the image can be easily confirmed before mounting the lithographic printing plate in a printing machine it can.
- an on-press development type or non-processing (non-development) type lithographic printing plate precursor without a conventional development processing step the image on the lithographic printing plate precursor is confirmed at the stage of mounting the lithographic printing plate precursor on a printing machine It is difficult, and it is not possible to print enough.
- an on-press development type or non-treatment (non-development) type planographic printing plate precursor a means for confirming an image at the exposed stage without adversely affecting on-press development, ie, the exposed area is colored or decolored It is required that a so-called printout image be formed.
- a photoacid generator and an acid chromogenic dye are contained in the image recording layer, and the acid chromogenic dye is produced by the action of an acid generated from the photoacid generator upon image exposure.
- an acid chromogenic dye leuco dye
- the lithographic printing plate precursor has high heat aging stability.
- the heat aging stability is low, dark polymerization proceeds in the lithographic printing plate precursor due to heat aging, and as a result, the on-press developability is reduced.
- an acid color-forming dye such as leuco dye
- the heat stability over time is an important characteristic for a lithographic printing plate precursor.
- An object of the present invention is to provide a curable composition capable of producing a lithographic printing plate precursor having excellent on-press developability. Another object of the present invention is to provide a curable composition having high heat aging stability. Another object of the present invention is to provide a lithographic printing plate precursor capable of producing a lithographic printing plate having high thermal aging stability, excellent on-press developability, and excellent printing durability. Still another object of the present invention is to provide a lithographic printing plate precursor capable of producing a lithographic printing plate having high thermal stability over time, excellent in plate inspection properties and on-press developability, and having excellent printing durability. It is to be.
- Cy 1 and Cy 2 which may be the same or different, each represents a ring structure formed together with a boron atom, an oxygen atom and Y, and each Y independently represents —O— or —NR 5 And R 5 represents a hydrogen atom, an alkylcarbonyl group, an arylcarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkoxycarbonyl group, an aryl group or a heteroaryl group.
- the ring structure represented by Cy 1 is selected from the group consisting of an alkylamide group, an alkenylamide group, an arylamide group, an alkylurea group, an arylurea group, a group having a sulfonamide structure, and a group having a sulfoneimide structure
- the ring structure represented by the above Cy 2 is an alkylamide group, an alkenylamide group, an arylamide group, an alkylurea group, an arylurea group, a sulfonamide structure
- the aromatic ring is condensed with an aromatic ring having at least one group selected from the group consisting of: and a group having a sulfoneimide structure.
- R 7 to R 14 may be the same or different and each independently represent a hydrogen atom, an alkyl group, an alkylamide group, an alkenylamide group, an arylamide group, an alkylurea group, an arylurea group, It represents a group having a sulfonamide structure or a group having a sulfonimide structure.
- At least one of R 7 to R 10 represents an alkylamide group, an alkenylamide group, an arylamide group, an alkylurea group, an arylurea group, a group having a sulfonamide structure, or a group having a sulfoneimide structure
- At least one of R 11 to R 14 represents an alkylamide group, an alkenylamide group, an arylamide group, an alkylurea group, an arylurea group, a group having a sulfonamide structure, or a group having a sulfoneimide structure.
- a curable composition comprising (A) an organic anion having a sulfonamide anion structure bound to a ring or a sulfoneimide anion structure bound to a ring, and (B) a salt compound having a counter cation.
- Cy represents an aryl group, a heteroaryl group, or an alicyclic group which may have an unsaturated bond.
- X represents an alkyl group, an aryl group, a heteroaryl group, SO 2 R a , SOR b , COR c , PO 3 R d , PO (R e ) (R f ), or H.
- R a , R b , R c , R d , R e and R f each represent a group selected from the group consisting of an alkyl group, an alkoxy group, an aryl group, a heteroaryl group, and H.
- R a , R b , R c , R d , R e or R f may be combined with Cy to form a ring.
- Cy represents an aryl group, a heteroaryl group, or an alicyclic group which may have an unsaturated bond.
- R a represents a group selected from the group consisting of an alkyl group, an alkoxy group, an aryl group, a heteroaryl group, and H. R a may combine with Cy to form a ring.
- R 1 to R 10 each independently represent a hydrogen atom or a monovalent substituent.
- R 11 to R 14 each independently represent a hydrogen atom or a monovalent substituent.
- a lithographic printing plate precursor having an image recording layer containing the curable composition according to any one of [1] to [19] on a support.
- R 1 to R 10 each independently represent a hydrogen atom or a monovalent substituent.
- R 11 to R 14 each independently represent a hydrogen atom or a monovalent substituent.
- R 1 to R 10 each independently represent a hydrogen atom or a monovalent substituent.
- R 11 to R 14 each independently represent a hydrogen atom or a monovalent substituent.
- a curable composition capable of producing a lithographic printing plate precursor having excellent on-press developability can be provided. Furthermore, according to the present invention, a curable composition having high heat aging stability can be provided. Further, according to the present invention, it is possible to provide a lithographic printing plate precursor capable of producing a lithographic printing plate having high thermal temporal stability, excellent in on-press developability, and excellent printing durability. Furthermore, according to the present invention, there is provided a lithographic printing plate precursor capable of producing a lithographic printing plate having high thermal stability over time, being excellent in plate inspection properties and on-press developability, and having excellent printing durability. be able to.
- a lithographic printing plate precursor capable of producing a lithographic printing plate having high heat aging stability and excellent printing durability. Furthermore, according to the present invention, it is possible to provide a method of preparing a lithographic printing plate using the above-mentioned lithographic printing plate precursor, and a compound used for the image recording layer of the above-mentioned lithographic printing plate precursor.
- the weight average molecular weight (Mw) in the present invention is gel permeation chromatography (GPC) using a column of TSKgel GMHxL, TSKgel G4000HxL, TSKgel G2000HxL (all are trade names manufactured by Tosoh Corp.) unless otherwise noted. 2.) It is a molecular weight which is detected by a solvent THF (tetrahydrofuran) and a differential refractometer by an analyzer and converted using polystyrene as a standard substance.
- THF tetrahydrofuran
- R represents an alkyl group, an aryl group or a monovalent heterocyclic group
- R represents an unsubstituted alkyl group, a substituted alkyl group, an unsubstituted aryl group, a substituted aryl group
- process is included in the term if the intended purpose of the process is achieved, even if it can not be clearly distinguished from other processes, as well as independent processes.
- the curable composition of the present invention is a) an organic anion having a ⁇ value of 16 or more, ⁇ p of 16 or more and 32 or less, and ⁇ H of 60% or less of ⁇ p in the SP value parameter of Hansen (hereinafter referred to as “ and b) a salt compound having a counter cation (hereinafter, also referred to as a “parameter-defining compound”).
- the units of ⁇ d, ⁇ p, and ⁇ H are MPa 0.5 .
- the curable composition (also referred to as "first curable composition") according to the first aspect of the present invention can produce a lithographic printing plate precursor having excellent on-press developability by the above configuration.
- first curable composition the curable composition
- the present invention generally has a large difference between the solubility parameter (SP value) of the ink and the solubility parameter (SP value) of water. Therefore, the non-image area of the image forming layer to be removed in the on-press development is originally exposed to an environment which is difficult to be compatible with each of the ink and the dampening water, and this decreases the on-press developability. I speculated that it was a factor.
- the dissolution parameter of Hansen may be mentioned.
- ⁇ d contributing to dispersibility, ⁇ p contributing to polarity, and ⁇ H contributing to hydrogen bond are known.
- the present inventors have developed an on-press development of a lithographic printing plate precursor by incorporating a specific salt compound having an organic anion defined using these three parameters into the curable composition. It is found that the solution is improved, and the above configuration is completed. Specifically, first, by setting ⁇ d in the organic anion of the above-mentioned salt compound to 16 or more, due to the interaction between the lipophilic group and the lipophilic group possessed by each other, among the salt compounds, etc.
- the intermolecular force can be easily reduced by, for example, relaxing the interaction during the on-press development while keeping the image forming layer in a desired state. It is considered to be a thing. Further, by setting ⁇ p in the organic anion of the above-mentioned salt compound to 16 or more, by raising the polarity of this salt compound, at the time of on-press development, the non-image area of the image forming layer is also exposed to water. It is considered to be compatible.
- the present inventors simply do not have to include a salt compound having an organic anion having a ⁇ p of 16 or more, and first, it is necessary to set ⁇ p to 32 or less. I found that. This is presumed to be due to the fact that if the polarity of the salt compound is too high, the non-affinity to the ink becomes large, and as a result, removal of the non-image area does not proceed smoothly. In addition, as a result of intensive studies, the present inventors have found that ⁇ H needs to be 60% or less of ⁇ p.
- ⁇ H is set to a fixed value or less with respect to ⁇ p, ie, by hydrogen bonding It is surmised that raising the polarity of the above-mentioned salt compound while making the contribution below a certain level is necessary for the removal of the non-image area and hence the improvement of the on-press developability.
- the above-mentioned salt compounds have the property of being selectively solvated with the ink and dampening water present at the time of on-press development of the lithographic printing plate precursor, and thus, both of the ink and dampening water. It is considered to have an affinity for it.
- the curable composition according to the first aspect of the present invention can produce a lithographic printing plate precursor having excellent on-press developability.
- the ⁇ d, ⁇ p and ⁇ H in the Hansen SP value parameter can be calculated respectively by the commercially available Hansen Solubility Parameter software (Hansen Solubility Parameter in Practice version 4.1. 07).
- the ⁇ d in the Hansen SP value parameter is 16 or more, preferably 18 or more, and more preferably 20 or more.
- the upper limit value of ⁇ d in the Hansen SP value parameter is not particularly limited, but is preferably 32 or less, more preferably 28 or less.
- ⁇ p is 16 or more and 32 or less, preferably 18 or more and 30 or less, and more preferably 20 or more and 28 or less.
- ⁇ H in the Hansen SP value parameter is 60% or less of ⁇ p, preferably 55% or less of ⁇ p, and more preferably 50% or less of ⁇ p. 20% or more of ⁇ p is preferable, and 30% or more of ⁇ p is more preferable.
- the salt compound contained in the curable composition according to the first aspect of the present invention is a compound in which a) an organic anion and b) a counter cation are bonded by an ionic bond.
- the a) organic anion is an aromatic ring or an aromatic ring in the molecule from the viewpoint of easily satisfying the above-mentioned “ ⁇ d in the Hansen SP value parameter is 16 or more, ⁇ p is 16 or more and 32 or less, ⁇ H is 60% or less of ⁇ p”. It is preferable that it is an organic anion having a heterocycle.
- the aromatic ring is specifically an aromatic hydrocarbon ring, and the aromatic hydrocarbon ring includes an aromatic hydrocarbon ring having 6 to 20 carbon atoms, and specifically, benzene, naphthalene, anthraquinone and the like Can be mentioned.
- the heterocycle is a heterocycle containing at least one hetero atom selected from an oxygen atom, a sulfur atom and a nitrogen atom.
- the heterocyclic ring is preferably a 5- to 8-membered ring.
- the heterocycle may be saturated or unsaturated.
- the heterocycle is preferably an aromatic heterocycle. Examples of the heterocyclic ring include pyridine ring, pyrimidine ring, pyrroline ring and the like.
- the parameter defining compound is not particularly limited as long as the organic anion satisfies the requirements of “ ⁇ d of 16 or more, ⁇ p of 16 or more and 32 or less, ⁇ H of 60% or less of ⁇ p in Hansen's SP value parameter”.
- the organic anion is preferably an organic anion having a sulfonamide anion structure bonded to the (A) ring or a sulfoneimide anion structure bonded to the ring, whereby the above requirements can be easily satisfied.
- bonded with a ring is as below-mentioned.
- the a) organic anion is also preferably a borate anion, and particularly preferably an organic anion represented by the following formula (V).
- V organic anion represented by the following formula (V).
- Cy 1 and Cy 2 which may be the same or different, each represents a ring structure formed together with a boron atom, an oxygen atom and Y, and each Y independently represents —O— or —NR 5 And R 5 represents a hydrogen atom, an alkylcarbonyl group, an arylcarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkoxycarbonyl group, an aryl group or a heteroaryl group.
- the ring structure represented by Cy 1 is selected from the group consisting of an alkylamide group, an alkenylamide group, an arylamide group, an alkylurea group, an arylurea group, a group having a sulfonamide structure, and a group having a sulfoneimide structure
- the ring structure represented by the above Cy 2 is an alkylamide group, an alkenylamide group, an arylamide group, an alkylurea group, an arylurea group, a sulfonamide structure
- the aromatic ring is condensed with an aromatic ring having at least one group selected from the group consisting of: and a group having a sulfoneimide structure. Examples of the aromatic ring include benzene ring, naphthalene ring and anthracene ring.
- the atomic chain constituting the ring structure represented by Cy1 or Cy2 is, for example, -O-C-C-O-, -O-C-C-C-O-, -O-C It is represented by —C—NR 5 —, —O—C—C—C—NR 5 —.
- both —O— or —NR 5 — at both ends are directly bonded to the boron atom.
- Examples of the aromatic ring fused to two adjacent carbon atoms include the above-mentioned aromatic rings.
- the aromatic ring is at least one group selected from the group consisting of an alkylamide group, an alkenylamide group, an arylamide group, an alkylurea group, an arylurea group, a group having a sulfonamide structure, and a group having a sulfoneimide structure Have.
- the aromatic ring may have a substituent, and examples of the substituent include an alkyl group and the like.
- Y is preferably -O-.
- Examples of the ring structure represented by Cy1 or Cy2 include a ring structure formed from catechol, salicylic acid, an oxalic acid derivative and a central atom B, and the like.
- the ring structure represented by Cy 1 is selected from the group consisting of an alkylamide group, an alkenylamide group, an arylamide group, an alkylurea group, an arylurea group, a group having a sulfonamide structure, and a group having a sulfoneimide structure
- the ring structure represented by the above Cy 2 is an alkylamide group, an alkenylamide group, an arylamide group, an alkylurea group, an arylurea group, a sulfonamide structure
- the aromatic ring is condensed with an aromatic ring having at least one group selected from the group consisting of: and a group having a sulfoneimide structure.
- an alkylamide In at least one group selected from the group consisting of an alkylamide group, an alkenylamide group, an arylamide group, an alkylurea group, an arylurea group, a group having a sulfonamide structure, and a group having a sulfoneimide structure, an alkylamide
- the alkyl group in the group and the alkyl group in the alkylurea group are preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and still more preferably an alkyl having 1 to 4 carbon atoms.
- the alkyl group may be linear or branched.
- alkyl group examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, ter-butyl, pentyl, isopentyl, hexyl, octyl, ter-octyl Groups, nonyl groups, decyl groups, dodecyl groups and the like.
- the alkyl group may have a substituent, and examples of the substituent include an alkoxy group, an aryloxy group, an aryl group, an alkoxycarbonyl group, a cyano group and the like.
- an alkenylamide in at least one group selected from the group consisting of an alkylamide group, an alkenylamide group, an arylamide group, an alkylurea group, an arylurea group, a group having a sulfonamide structure, and a group having a sulfoneimide structure, an alkenylamide
- the alkenyl group in the group is preferably an alkenyl group having 2 to 12 carbon atoms, and more preferably an alkenyl group having 2 to 6 carbon atoms.
- the alkenyl group may be linear or branched. Examples of alkenyl groups include ethenyl group, propenyl group and the like.
- the alkenyl group may have a substituent, and examples of the substituent include an alkoxy group, an alkylcarbonyl group and the like.
- an arylamide In at least one group selected from the group consisting of an alkylamide group, an alkenylamide group, an arylamide group, an alkylurea group, an arylurea group, a group having a sulfonamide structure, and a group having a sulfoneimide structure, an arylamide
- the aryl group in the group and the aryl group in the arylurea group are preferably aryl groups having 6 to 20 carbon atoms, and more preferably aryl groups having 6 to 10 carbon atoms. Examples of the aryl group include phenyl group and naphthyl group.
- the aryl group may have a substituent, and examples of the substituent include an alkyl group, an alkoxy group, an aryloxy group, an aryl group, an alkoxycarbonyl group, a cyano group, an amide group, a urea group, a halogen atom and the like It can be mentioned.
- sulfonamide structure in the group having a structure represents the following structure.
- * represents a bond.
- sulfoneimide In at least one group selected from the group consisting of an alkylamide group, an alkenylamide group, an arylamide group, an alkylurea group, an arylurea group, a group having a sulfonamide structure, and a group having a sulfoneimide structure, sulfoneimide
- the sulfone imide structure in the group having a structure represents the following structure. In the following structure, * represents a bond.
- the a) organic anion is preferably an organic anion represented by the following formula (VI).
- R 7 to R 14 may be the same or different and each independently represent a hydrogen atom, an alkyl group, an alkylamide group, an alkenylamide group, an arylamide group, an alkylurea group, an arylurea group, It represents a group having a sulfonamide structure or a group having a sulfonimide structure.
- At least one of R 7 to R 10 represents an alkylamide group, an alkenylamide group, an arylamide group, an alkylurea group, an arylurea group, a group having a sulfonamide structure, or a group having a sulfoneimide structure
- At least one of R 11 to R 14 represents an alkylamide group, an alkenylamide group, an arylamide group, an alkylurea group, an arylurea group, a group having a sulfonamide structure, or a group having a sulfoneimide structure.
- the alkyl group as R 7 to R 14 is selected from the group consisting of an alkylamide group, an alkenylamide group, an arylamide group, an alkylurea group, an arylurea group, a group having a sulfonamide structure, and a group having a sulfoneimide structure
- an alkylamide group and the alkyl group in the alkylurea group in the ring structure represented by the above Cy 1 which is condensed with an aromatic ring having at least one group .
- the group having an alkylamide group, an alkenylamide group, an arylamide group, an alkylurea group, an arylurea group, a sulfonamide structure, or a group having a sulfoneimide structure has a ring structure represented by the above Cy1 or Cy2, respectively.
- an alkylamide group an alkenylamide group, an arylamide group, an alkylurea group, an arylurea group, a group having a sulfonamide structure, and a group having a sulfoneimide structure, which an aromatic ring to be fused has It is the same as the group having an alkylamide group, an alkenylamide group, an arylamide group, an alkylurea group, an arylurea group, a sulfonamide structure, and a group having a sulfoneimide structure in at least one group, and preferred ranges are also the same. is there.
- Ratio (%) of ⁇ d, ⁇ p, ⁇ H, and ⁇ H to ⁇ p in Hansen's SP value parameters of B-1, B-2, B-3, B-4, and B-5 above (( ⁇ H / ⁇ p) ⁇ 100) are listed in the table below.
- the parameter defining compounds according to the present invention may be used singly or in combination of two or more.
- the first composition of the present invention has the same content as the specific compound described later.
- the curable composition of the present invention is an organic anion having a sulfonamide anion structure attached to the (A) ring or a sulfoneimide anion structure attached to the ring (hereinafter "(A) organic anion” or " And a salt compound having a counter cation.
- the salt compound (hereinafter, also simply referred to as “specific compound”) contained in the curable composition of the present invention is (A) an organic anion and (B) counter It is a compound in which a cation is bound by an ionic bond.
- the sulfonamide anion structure in the (A) organic anion represents an anion structure in which a hydrogen atom is removed from the following sulfonamide structure.
- * represents a bond.
- the sulfone imide anion structure in the (A) organic anion represents an anion structure in which a hydrogen atom is removed from the following sulfonimide structure.
- * represents a bond.
- the (A) organic anion in the present invention is one in which a negative charge is present on a nitrogen atom, but it may also be described, for example, by a resonance structure, and may be a structure in which a negative charge is present in addition to a nitrogen atom.
- a resonance structure for example, the resonance structure in the sulfoneimide anion is described below as an example.
- the (A) organic anion in the present invention may have a sulfonamide anion structure or a form having one sulfoneimide anion structure, or may have a form having two or more.
- ring in the organic anion which comprises the specific compound which concerns on this invention is not specifically limited, An aromatic hydrocarbon ring, an alicyclic hydrocarbon ring, or a heterocyclic ring etc. are mentioned.
- the aromatic hydrocarbon ring includes an aromatic hydrocarbon ring having 6 to 20 carbon atoms, and specific examples include benzene, naphthalene, anthraquinone and the like.
- the alicyclic hydrocarbon ring includes an alicyclic hydrocarbon ring having 3 to 30 carbon atoms.
- the alicyclic hydrocarbon ring may have an unsaturated bond.
- the heterocycle is a heterocycle containing at least one hetero atom selected from an oxygen atom, a sulfur atom and a nitrogen atom.
- the heterocyclic ring is preferably a 5- to 8-membered ring.
- the heterocycle may be saturated or unsaturated.
- the heterocycle is preferably an aromatic heterocycle. Examples of the heterocyclic ring include pyridine ring, pyrimidine ring, pyrroline ring and the like.
- the (A) organic anion in the present invention is preferably an organic anion represented by the following general formula (I).
- the organic anion according to the present invention can be represented by a plurality of resonant structural formulas according to the electron configuration as in the general anion, but in the present specification, as shown below, the negative charge on the nitrogen atom It describes using the resonance structural formula which has.
- Cy represents an aryl group, a heteroaryl group, or an alicyclic group which may have an unsaturated bond.
- X represents an alkyl group, an aryl group, a heteroaryl group, SO 2 R a , SOR b , COR c , PO 3 R d , PO (R e ) (R f ), or H.
- R a , R b , R c , R d , R e and R f each represent a group selected from the group consisting of an alkyl group, an alkoxy group, an aryl group, a heteroaryl group, and H.
- R a , R b , R c , R d , R e or R f may combine with Cy to form a ring.
- the aryl group represented by Cy is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, and still more preferably an aryl group having 6 to 10 carbon atoms.
- a phenyl group, a naphthyl group, etc. are mentioned, A phenyl group etc. are preferable.
- the heteroaryl group represented by Cy is a group formed from a heterocycle containing at least one hetero atom selected from an oxygen atom, a sulfur atom and a nitrogen atom.
- the heterocycle is preferably a 5- to 8-membered ring, more preferably a 5- to 6-membered ring.
- Examples of the heteroaryl group include pyridyl group, pyrimidyl group, pyrrolyl group, furanyl group, imidazolyl group, pyrazolyl group, triazolyl group, tetrazolyl group, indolyl group, quinolinyl group, oxadiazolyl group, benzoxazolyl group and the like. .
- the alicyclic group represented by Cy is a group formed from an alicyclic ring having 3 to 30 carbon atoms, preferably an alicyclic ring having 4 to 9 carbon atoms.
- the alicyclic ring may be monocyclic or polycyclic.
- the alicyclic ring may have an unsaturated bond.
- Examples of the alicyclic group which may have an unsaturated bond include cyclopentanyl group, cyclopentadienyl group, cyclohexenyl group, cyclohexadienyl group, cycloheptanyl group, cycloheptadienyl group, norbornene group and the like It can be mentioned.
- the above aryl group, heteroaryl group or heteroaryl group may have a substituent, and examples of the substituent include an alkyl group, an alkoxy group, an aryloxy group, an aryl group, a carbonyl group and an alkoxycarbonyl group. , Cyano group, amido group, urea group, urethane group, alkenyl group, allyl group, acryl group, acryl group, methacryl group, acrylamide group, methacrylamide group, a group formed by combining one or more of halogen atoms, etc.
- the alkyl group represented by X is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and still more preferably an alkyl group having 1 to 8 carbon atoms.
- the group may be linear or branched.
- alkyl group examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, octyl and tert-octyl Groups, nonyl groups, decyl groups, dodecyl groups, ethylhexyl groups and the like.
- the alkyl group is preferably a methyl group, an ethyl group or a tert-butyl group.
- aryl group and heteroaryl group represented by X in Formula (I) have the same meanings as the aryl group and heteroaryl group represented by Cy in Formula (I), and the preferred range is also the same.
- the alkyl group, aryl group and heteroaryl group represented by Ra , Rb , Rc , Rd , Re and Rf are represented by X in formula (I)
- the alkoxy group represented by R a , R b , R c , R d , R e and R f in the formula (I) is preferably an alkoxy group having 1 to 20 carbon atoms, and is preferably an alkoxy having 1 to 16 carbon atoms The group is more preferable, and the alkoxy group having 1 to 12 carbon atoms is further preferable.
- the alkyl group, aryl group or heteroaryl group represented by X above may have a substituent, and examples of the substituent include an alkyl group, an alkoxy group, an aryloxy group, an aryl group and a carbonyl group. , Alkoxycarbonyl group, cyano group, amido group, urea group, urethane group, alkenyl group, allyl group, acryl group, acryl group, methacryl group, acrylamide group, methacrylamide group, halogen atom, or two or more of them are combined Groups and the like.
- the alkyl group, alkoxy group, aryl group or heteroaryl group represented by Ra , Rb , Rc , Rd , Re , Rf and Rg may have a substituent.
- substituents include an alkyl group, an alkoxy group, an aryloxy group, an aryl group, a carbonyl group, an alkoxycarbonyl group, a cyano group, an amido group, a urea group, a urethane group, an alkenyl group, an allyl group, an acrylic group and a methacryl group.
- substituent include groups in which one or two or more of a group, an acrylamide group, a methacrylamide group, and a halogen atom are combined.
- an alkyl group, a heteroaryl group, SO 2 R a , SOR b , COR c , PO 3 R d , PO (R e ) (R f ) or H is preferable.
- R a , R b , R c , R d , R e or R f may combine with Cy to form a ring.
- R a is SO 2 R a
- R a is H (hydrogen atom)
- R a is bonded to Cy to form a ring
- H as R a is eliminated and SO 2 is C y It represents that it combines with.
- the (A) organic anion in the present invention is preferably an organic anion represented by the following general formula (II).
- Cy represents an aryl group, a heteroaryl group, or an alicyclic group which may have an unsaturated bond.
- R a represents a group selected from the group consisting of an alkyl group, an alkoxy group, an aryl group, a heteroaryl group, and H. R a may combine with Cy to form a ring.
- an aryl group represented by Cy, a heteroaryl group and an alicyclic group which may have an unsaturated bond are an aryl group represented by Cy in the formula (I), a hetero group It is synonymous with an aryl group and an alicyclic group which may have an unsaturated bond, and preferred ranges are also synonymous.
- the aryl group, heteroaryl group or heteroaryl group represented by Cy above may have a substituent, and examples of the substituent include an alkyl group, an alkoxy group, an aryloxy group, an aryl group, a carbonyl Or one or more of a group, alkoxycarbonyl group, cyano group, amido group, urea group, urethane group, alkenyl group, allyl group, acryl group, acryl group, methacryl group, acrylamide group, methacrylamide group, halogen atom And the like.
- Ra in the general formula (II) is the same as Ra in X in the general formula (I), and the preferred range is also the same.
- the alkyl group, alkoxy group, aryl group or heteroaryl group represented by R a may have a substituent, and examples of the substituent include an alkyl group, an alkoxy group, an aryloxy group, an aryl Group, carbonyl group, alkoxycarbonyl group, cyano group, amido group, urea group, urethane group, alkenyl group, allyl group, acryl group, acryl group, methacryl group, acrylamide group, methacrylamide group, halogen atom, one or more of And the like.
- the (A) organic anion in the present invention is preferably an organic anion represented by the following general formula (III) or (IV).
- R 1 to R 10 each independently represent a hydrogen atom or a monovalent substituent.
- R 11 to R 14 each independently represent a hydrogen atom or a monovalent substituent.
- the monovalent substituent represented by R 1 to R 10 in general formula (III) is not particularly limited as long as the effects of the present invention are not impaired.
- An alkyl group of 12 is preferable, an alkyl group having 1 to 10 carbon atoms is more preferable, and an alkyl group having 1 to 8 carbon atoms is further preferable.
- the alkyl group may be linear or branched, an alkoxy group (alkoxy).
- the alkyl group in the group is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and still more preferably an alkyl group having 1 to 8 carbon atoms.
- aryloxy group (the aryl group in the aryloxy group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, and 6 to 10 carbon atoms A reel group is more preferable), an aryl group (an aryl group having 6 to 20 carbon atoms is preferable, an aryl group having 6 to 15 carbon atoms is more preferable, and an aryl group having 6 to 10 carbon atoms is further preferable), a carbonyl group And the alkoxycarbonyl group (The alkyl group in the alkoxy group is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and still more preferably an alkyl group having 1 to 8 carbon atoms.
- It may be linear or branched), cyano group, amido group, urea group, urethane group, alkenyl group (preferably, alkenyl group having 2 to 15, more preferably 2 to 6 carbon atoms), allyl group, acrylic Group, methacryl group, acrylamide group, methacrylamide group, one of halogen atoms (fluorine atom, chlorine atom, bromine atom or iodine atom) or And a group of two or more is formed by combining the like.
- the group mentioned as the monovalent substituent may be further substituted by another group.
- the monovalent substituent represented by R 11 to R 14 in the general formula (IV) is not particularly limited as long as the effects of the present invention are not impaired.
- An alkyl group of 12 is preferable, an alkyl group having 1 to 10 carbon atoms is more preferable, and an alkyl group having 1 to 8 carbon atoms is further preferable.
- the alkyl group may be linear or branched, an alkoxy group (alkoxy).
- the alkyl group in the group is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and still more preferably an alkyl group having 1 to 8 carbon atoms.
- aryloxy group (the aryl group in the aryloxy group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, and 6 to 10 carbon atoms An aryl group is more preferable), an aryl group (an aryl group having 6 to 20 carbon atoms is preferable, an aryl group having 6 to 15 carbon atoms is more preferable, and an aryl group having 6 to 10 carbon atoms is further preferable), a carbonyl group And the alkoxycarbonyl group (The alkyl group in the alkoxy group is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and still more preferably an alkyl group having 1 to 8 carbon atoms.
- It may be linear or branched), cyano group, amido group, urea group, urethane group, alkenyl group (preferably, alkenyl group having 2 to 15, more preferably 2 to 6 carbon atoms), allyl group, acrylic Group, methacryl group, acrylamide group, methacrylamide group, one of halogen atoms (fluorine atom, chlorine atom, bromine atom or iodine atom) or And groups in which two or more are combined, and the like.
- the group mentioned as the monovalent substituent may be further substituted by another group.
- the ratio (%) of ⁇ d, ⁇ p, ⁇ H and ⁇ H to ⁇ p in the Hansen SP value parameters of the above I-1 to I-15, I-17 to I-21, and I-23 to I-25 (( ⁇ H / ⁇ p) ⁇ 100) is described in the table below.
- ⁇ d in the Hansen SP value parameter can easily satisfy the requirements of 16 or more, ⁇ p of 16 or more and 32 or less, and ⁇ H of 60% or less of ⁇ p, as a) organic anion, It is preferable that it is the organic anion represented.
- Cy 1 represents an aryl group or a heteroaryl group.
- X 1 represents SO 2 R a , SOR b , COR c , PO 3 R d , or PO (R e ) (R f ).
- R a , R b , R c , R d , R e and R f each represent a group selected from the group consisting of an alkyl group, an alkoxy group, an aryl group, a heteroaryl group, and H.
- R a , R b , R c , R d , R e or R f may combine with Cy 1 to form a ring.
- the aryl group and the heteroaryl group in Cy 1 are the same as the aryl group and the heteroaryl group in Cy, and the preferable range is also the same.
- the organic anion represented by the following general formula (IA) as the organic anion a) in the present invention is preferably an organic anion represented by the above general formula (III) or (IV).
- the counter cation ((B) counter cation) constituting the specific compound according to the present invention may be a cation capable of forming a salt compound by an ionic bond with an organic anion in which a negative charge is present on the above aluminum atom or phosphorus atom.
- the counter cation may be an inorganic cation or an organic cation. Examples of the inorganic cation include alkali metal ions such as lithium ion, sodium ion and potassium ion, and alkaline earth metal ions such as calcium, magnesium ion and calcium ion.
- Organic cations include organic cations in which a positive charge is present on the nitrogen atom.
- the organic cation having a positive charge on the nitrogen atom is represented by the formula: N + (R 01 ) (R 02 ) (R 03 ) (R 04 ) (where R 01 , R 02 , R 03 , R 04 is And each independently represents an ammonium cation represented by an alkyl group or an aryl group, a pyridinium cation, an imidazolium cation and the like.
- ammonium cations include tetramethyl ammonium, tetraethyl ammonium, tetrabutyl ammonium and the like.
- the counter cation is preferably a diaryl iodonium cation or a triaryl sulfonium cation. Certain compounds having a diaryliodonium cation or triarylsulfonium cation as a counter cation are extremely useful as a photopolymerization initiator.
- the diaryl iodonium cation and the triaryl sulfonium cation respectively include, for example, an iodonium cation represented by the following formula (C1) and a sulfonium cation represented by (C2).
- Ar1, Ar2, Ar3, Ar4 and Ar5 each independently represent a group represented by formula (C3).
- R 20 represents an alkyl group, an alkoxy group, a vinyl group or a halogen atom, and a plurality of R 20 may be the same or different.
- l represents an integer of 0 to 5;
- diaryliodonium cation examples include diphenyliodonium cation, 4-methoxyphenyl-4- (2-methylpropyl) phenyliodonium cation, 4-chlorophenyl-4-phenyliodonium cation, 4- (2-methylpropyl) phenyl- p-Tolyliodonium cation, 4-hexyloxyphenyl-2,4,6-trimethoxyphenyliodonium cation, 4-hexyloxyphenyl-2,4-diethoxyphenyliodonium cation, 4-octyloxyphenyl-2,4, Examples include 6-trimethoxyphenyliodonium cation and bis (4-tert-butylphenyl) iodonium cation.
- triarylsulfonium cation examples include triphenylsulfonium cation, bis (4-chlorophenyl) phenylsulfonium cation, bis (4-chlorophenyl) -4-methylphenylsulfonium cation, tris (4-chlorophenyl) sulfonium cation, tris ( Examples include 2,4-dichlorophenyl) sulfonium cation, bis (2,4-dichlorophenyl) phenylsulfonium cation, and bis (2,4-dichlorophenyl) 4-methoxyphenylsulfonium cation.
- counter cations in cyanine dyes used as infrared absorbers are also useful.
- the counter cation in the cyanine dye will be described in the following description of the infrared absorber.
- the parameter defining compound of the present invention and the specific compound each consist of a combination of an anion moiety and a cation moiety, and the anion moiety and the cation moiety can be any combination of structures selected from the respective groups.
- Specific examples of the structures of the anion moiety and cation moiety are as described above, but the present invention is not limited thereto.
- the specific compound is represented in a form in which the anion part and the cation part are described as in I-1-j-1.
- the specific compounds according to the present invention may be used alone or in combination of two or more.
- the content of the specific compound largely varies depending on the structure of the specific compound, the intended effect, the use and the like.
- the total solid content of the composition is preferably 0.1 to 50% by mass, more preferably 0.5 to 40% by mass, and still more preferably 1 to 30% by mass.
- total solids content refers to the total amount of components excluding volatile components such as solvents in the composition of the present invention.
- the specific compound according to the present invention exhibits various effects.
- the composition of the present invention containing the specific compound has high heat aging stability (developability after forced heat aging). This is considered to be due to the excellent properties of the organic anion constituting the specific compound, and even when compared with the borate anion described in Patent Document 1, a remarkable improvement effect on the thermal temporal stability is recognized. Therefore, the lithographic printing plate precursor to which the composition of the present invention is applied also has excellent heat aging stability.
- the second composition of the present invention containing the specific compound is excellent in the electron transfer efficiency or the light-to-heat conversion efficiency from the infrared absorber resulting from the infrared exposure to the specific compound.
- a lithographic printing plate produced from a lithographic printing plate precursor to which the composition of the present invention is applied has excellent press life.
- the organic anion constituting the specific compound has a sulfonamide anion structure or a sulfoneimide anion structure having a negative charge on the nitrogen atom, and a relatively hydrophilic portion and a hydrophobic portion thereof, It is considered to have emulsifiability because it has a relatively hydrophobic moiety having a rigid ring structure.
- a lithographic printing plate precursor to which the composition of the present invention is applied exhibits good on-press developability. Furthermore, since the organic anion constituting the specific compound functions as an acid, a color image can be formed by using an acid color former such as a leuco dye in combination with the composition of the present invention as described later.
- the organic anion which comprises a specific compound is excellent in color development performance, therefore, for example, the lithographic printing plate precursor to which the composition of the present invention is applied exhibits excellent platemaking properties.
- a lithographic printing plate precursor wherein a polymerization initiator containing PF 6 ⁇ known as an inorganic anion is used in combination with an acid color former such as a leuco dye has a problem that ring-like coloring occurs with heat aging.
- the ring-like color development is a phenomenon in which fine ring-like color formation occurs over the entire surface of the lithographic printing plate precursor, which hinders the plate-making operation.
- PF 6 - in place of, the lithographic printing plate precursor of the polymerization initiator in combination with an acid color former such as a leuco dye containing an organic anion according to the present invention has the advantage that a thermal aging does not cause ring coloring.
- the invention also relates to specific compounds.
- specific compound include the following compounds. ⁇ 1> The compound whose organic anion is represented with the following general formula (III) or (IV), and whose counter cation is a diaryl iodonium cation and a triaryl sulfonium cation.
- R 1 to R 10 each independently represent a hydrogen atom or a monovalent substituent.
- R 11 to R 14 each independently represent a hydrogen atom or a monovalent substituent.
- R 1 to R 10 each independently represent a hydrogen atom or a monovalent substituent.
- R 11 to R 14 each independently represent a hydrogen atom or a monovalent substituent.
- Each group in General Formula (III) and (IV) is synonymous with each group mentioned above, respectively, and its preferable range is also synonymous.
- the diaryliodonium cation and the triarylsulfonium cation have the same meaning as the diaryliodonium cation and the triarylsulfonium cation described above, and the preferred ranges are also the same.
- the second composition of the present invention is preferably a composition of the following forms (1) to (3).
- the composition of form (1) comprises a specific compound, an infrared absorber, one or more of a binder polymer and polymer particles, and a polymerizable compound.
- the composition of the form (2) contains a specific compound, an acid color former, an infrared absorber, one or more of a binder polymer and polymer particles, and a polymerizable compound.
- the composition of the form (3) contains one or more of a specific compound, an acid color former, an infrared absorber, a binder polymer and polymer particles, a polymerizable compound, and a polymerization initiator.
- the specific compound in the composition of form (1) is preferably a polymerization initiator whose counter cation is a diaryliodonium cation or a triarylsulfonium cation.
- the specific compound in the composition of form (2) is preferably a polymerization initiator whose counter cation is a diaryliodonium cation or a triarylsulfonium cation.
- the specific compound in the composition of the form (3) is preferably an additive in which the counter cation is an alkali metal ion, an alkaline earth metal ion or an organic cation having a charge on a nitrogen atom.
- the composition of the present invention components that can be included in the first or second composition of the present invention (hereinafter, also collectively referred to as “the composition of the present invention”) will be described.
- the composition of the present invention preferably contains an infrared absorber.
- the infrared absorber has a function of being excited by infrared rays to perform electron transfer and / or energy transfer to a polymerization initiator or the like. It also has the function of converting the absorbed infrared radiation into heat.
- the infrared absorber preferably has maximum absorption in the wavelength range of 750 to 1,400 nm.
- a dye or a pigment is mentioned, and a dye is preferably used.
- dyes commercially available dyes and known dyes described in the literature such as "Dye Handbook” (edited by the Society of Synthetic Organic Chemistry, published in 1945) can be used. Specifically, dyes such as azo dyes, metal complex salt azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, cyanine dyes, squarylium dyes, pyrylium salts, metal thiolate complexes, etc. Can be mentioned. Among the dyes, cyanine dyes, squarylium dyes and pyrylium salts are preferable, cyanine dyes are more preferable, and indolenine cyanine dyes are particularly preferable.
- the compounds described in paragraph 0021 of EP 1736312 and the compounds described in paragraphs 0069 to 0080 of WO 2016/027886 can also be used.
- the cyanine dye include compounds described in paragraphs 0017 to 0019 of JP-A 2001-133969, paragraphs 0016 to 0021 of JP-A 2002-023360, and paragraphs 0012 to 0037 of JP-A 2002-040638.
- the compounds described in 0043 can be mentioned. Further, compounds described in paragraphs 0008 to 0009 of JP-A-5-5005 and paragraphs 0022 to 0025 of JP-A 2001-222101 can also be preferably used.
- the compounds described in paragraphs 0072 to 0076 of JP-A-2008-195018 are preferable.
- the cyanine dye can contain the organic anion according to the present invention as a counterion that neutralizes charge.
- the cyanine dye corresponds to the specific compound according to the present invention.
- the infrared absorbers may be used alone or in combination of two or more.
- the infrared absorbing agent can be contained in any amount in the composition.
- the content of the infrared absorber is preferably 0.05 to 30% by mass, more preferably 0.1 to 20% by mass, and still more preferably 0.2 to 10% by mass, in the total solid content of the composition.
- the composition of the present invention preferably contains a polymerizable compound.
- the polymerizable compound may be, for example, a radically polymerizable compound or a cationically polymerizable compound, but it is an addition polymerizable compound (ethylenically unsaturated compound) having at least one ethylenically unsaturated bond. Is preferred.
- ethylenically unsaturated compound a compound having at least one terminal ethylenic unsaturated bond is preferable, and a compound having two or more terminal ethylenic unsaturated bonds is more preferable.
- the polymerizable compound can have a chemical form such as, for example, a monomer, a prepolymer, that is, a dimer, a trimer or an oligomer, or a mixture thereof.
- the monomer examples include unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid), esters thereof and amides thereof.
- esters of unsaturated carboxylic acid and polyhydric alcohol compound, and amides of unsaturated carboxylic acid and polyhydric amine compound are used.
- addition reaction products of unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as hydroxy group, amino group and mercapto group with monofunctional or polyfunctional isocyanates or epoxies, and monofunctional or monofunctional Dehydration condensation products with polyfunctional carboxylic acids and the like are also suitably used.
- unsaturated carboxylic acid esters having an electrophilic substituent such as an isocyanate group and an epoxy group, or an addition reaction product of an amide with a monofunctional or polyfunctional alcohol, an amine or a thiol, and a halogen atom are also suitable.
- substitution products of unsaturated carboxylic acid esters or amides having a leaving substituent such as tosyloxy group and amides with monofunctional or polyfunctional alcohols, amines, and thiols.
- a compound group in which the above-mentioned unsaturated carboxylic acid is replaced by unsaturated phosphonic acid, styrene, vinyl ether and the like can also be used.
- monomers of esters of polyhydric alcohol compounds and unsaturated carboxylic acids include, as acrylic acid esters, ethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, and the like.
- examples thereof include trimethylolpropane triacrylate, hexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol tetraacrylate, sorbitol triacrylate, ethylene oxide (EO) modified triacrylate isocyanurate, and polyester acrylate oligomer.
- methacrylic acid ester As methacrylic acid ester, tetramethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, pentaerythritol trimethacrylate, bis [p- (3-methacryloxy-2-hydroxypropoxy) phenyl] Dimethylmethane, bis [p- (methacryloxyethoxy) phenyl] dimethylmethane and the like can be mentioned.
- monomers of amides of a polyvalent amine compound and an unsaturated carboxylic acid include methylenebisacrylamide, methylenebismethacrylamide, 1,6-hexamethylenebisacrylamide, 1,6-hexamethylenebismethacrylamide, Diethylene triamine tris acrylamide, xylylene bis acrylamide, xylylene bis methacrylamide etc. are mentioned.
- urethane addition polymerization compounds produced by using an addition reaction of an isocyanate and a hydroxy group are also suitable, and specific examples thereof include, for example, one molecule described in JP-B-48-41708.
- Vinyl containing two or more polymerizable vinyl groups in one molecule obtained by adding a hydroxyl group-containing vinyl monomer represented by the following formula (M) to a polyisocyanate compound having two or more isocyanate groups Urethane compounds and the like can be mentioned.
- CH 2 C (R M4 ) COOCH 2 CH (R M5 ) OH (M)
- R M4 and R M5 each independently represent a hydrogen atom or a methyl group.
- Urethane Compounds Having an Oxide-Based Skeleton, U.S. Pat. Nos. 7,153,632, JP-A-8-505,598, JP-A-2007-293221, JP-A-2007-293223, and Urethane Compounds Having a Hydrophilic Group are also suitable.
- the details of the method of use such as the structure of the polymerizable compound, single use or combined use, and the addition amount can be arbitrarily set in consideration of the final use of the composition and the like.
- the content of the polymerizable compound is preferably 5 to 75% by mass, more preferably 10 to 70% by mass, and still more preferably 15 to 60% by mass, based on the total solid content of the composition.
- the composition of the present invention preferably contains a polymerization initiator.
- the polymerization initiator is a compound that generates polymerization initiation species such as radicals and cations by light and / or heat energy, and known thermal polymerization initiators, compounds having a small bond dissociation energy, and photopolymerization initiators And so on.
- a polymerization initiator an infrared photosensitive polymerization initiator is preferable.
- a radical polymerization initiator is preferable.
- radical polymerization initiator examples include organic halides, carbonyl compounds, azo compounds, organic peroxides, metallocene compounds, azide compounds, hexaarylbiimidazole compounds, disulfone compounds, oxime ester compounds, and onium salt compounds.
- organic halide for example, compounds described in paragraphs 0022 to 0023 of JP-A-2008-195018 are preferable.
- carbonyl compound for example, compounds described in paragraph 0024 of JP-A-2008-195018 are preferable.
- azo compound include azo compounds described in JP-A-8-108621.
- organic peroxide for example, compounds described in paragraph 0025 of JP-A-2008-195018 are preferable.
- metallocene compound for example, the compounds described in paragraph 0026 of JP-A-2008-195018 are preferable.
- the azide compound include compounds such as 2,6-bis (4-azidobenzylidene) -4-methylcyclohexanone.
- hexaarylbiimidazole compound for example, compounds described in paragraph 0027 of JP-A-2008-195018 are preferable.
- disulfone compound examples include compounds described in JP-A-61-166544 and JP-A-2002-328465.
- oxime ester compound for example, compounds described in paragraphs 0028 to 0030 of JP-A-2008-195018 are preferable.
- oxime esters and onium salts are more preferable from the viewpoint of curability, and onium salts such as iodonium salts, sulfonium salts and azinium salts are further preferable.
- onium salts such as iodonium salts, sulfonium salts and azinium salts are further preferable.
- iodonium salts and sulfonium salts are particularly preferred. Specific examples of iodonium salts and sulfonium salts are shown below, but the present invention is not limited thereto.
- diphenyliodonium salt is preferable, and in particular, diphenyliodonium salt having an electron donating group as a substituent, for example, diphenyliodonium salt substituted with an alkyl group or an alkoxyl group is preferable, and asymmetric diphenyliodonium salt is also preferable. preferable.
- sulfonium salts are preferably triarylsulfonium salts, particularly preferably triarylsulfonium salts having an electron withdrawing group as a substituent, for example, a triarylsulfonium salt in which at least a part of the group on the aromatic ring is substituted with a halogen atom.
- triarylsulfonium salts in which the total substitution number of halogen atoms on the aromatic ring is 4 or more are more preferable.
- triphenylsulfonium hexafluorophosphate
- triphenylsulfonium benzoyl formate
- bis (4-chlorophenyl) phenylsulfonium benzoyl formate
- bis (4-chlorophenyl) -4-methylphenylsulfonium tetrafluoro Borate
- tris (4-chlorophenyl) sulfonium 3,5-bis (methoxycarbonyl) benzenesulfonate
- tris (4-chlorophenyl) sulfonium hexafluorophosphate
- the polymerization initiator can contain the organic anion according to the present invention as an anion.
- the polymerization initiator corresponds to the specific compound according to the present invention.
- the polymerization initiator may be used alone or in combination of two or more.
- the content of the polymerization initiator is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, and still more preferably 0.8 to 20% by mass, based on the total solid content of the composition.
- the composition of the present invention preferably contains a binder polymer.
- a binder polymer polymers having film properties are preferable, and known binder polymers used in the composition can be suitably used.
- the binder polymer (meth) acrylic resin, polyvinyl acetal resin and polyurethane resin are preferable.
- a known binder polymer used in the image recording layer of the lithographic printing plate precursor can be suitably used as the binder polymer.
- a binder polymer hereinafter, also referred to as a binder polymer for on-press development
- a binder polymer for on-press development a binder polymer having an alkylene oxide chain is preferable.
- the binder polymer having an alkylene oxide chain may have a poly (alkylene oxide) moiety in the main chain or in the side chain.
- it may be a graft polymer having a poly (alkylene oxide) in a side chain, or a block copolymer of a block constituted by a poly (alkylene oxide) -containing repeating unit and a block constituted by a (alkylene oxide) non-containing repeating unit.
- a polyurethane resin is preferred.
- the polymer of the main chain when having a poly (alkylene oxide) moiety in the side chain includes (meth) acrylic resin, polyvinyl acetal resin, polyurethane resin, polyurea resin, polyimide resin, polyamide resin, epoxy resin, polystyrene resin, novolac type Phenol resin, polyester resin, synthetic rubber, natural rubber are mentioned, and (meth) acrylic resin is particularly preferable.
- alkylene oxide an alkylene oxide having 2 to 6 carbon atoms is preferable, and ethylene oxide or propylene oxide is particularly preferable.
- the number of repeating alkylene oxides in the poly (alkylene oxide) moiety is preferably 2 to 120, more preferably 2 to 70, and still more preferably 2 to 50. If the number of repetitions of the alkylene oxide is 120 or less, both of the printing durability due to abrasion and the printing durability due to ink receptivity do not deteriorate, which is preferable.
- the poly (alkylene oxide) moiety is preferably contained as a side chain of the binder polymer in a structure represented by the following formula (AO), and as a side chain of a (meth) acrylic resin, it is represented by the following formula (AO) More preferably, it is contained in the following structure.
- y represents 2 to 120
- R 1 represents a hydrogen atom or an alkyl group
- R 2 represents a hydrogen atom or a monovalent organic group.
- the monovalent organic group an alkyl group having 1 to 6 carbon atoms is preferable.
- y is preferably 2 to 70, and more preferably 2 to 50.
- R 1 is preferably a hydrogen atom or a methyl group, particularly preferably a hydrogen atom.
- R 2 is particularly preferably a hydrogen atom or a methyl group.
- the binder polymer 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 or may be introduced by a polymer reaction.
- Examples of polymers having an ethylenically unsaturated bond in the main chain of the molecule include poly-1,4-butadiene, poly-1,4-isoprene and the like.
- An example of a polymer having an ethylenically unsaturated bond in the side chain of the molecule is a polymer of an ester or amide of acrylic acid or methacrylic acid, and the residue of ester or amide (R of -COOR or -CONHR) is Mention may be made of polymers having ethylenically unsaturated bonds.
- free radicals polymerization initiating radicals or propagating radicals in the polymerization process of the polymerizable compound
- Addition polymerization is performed to form crosslinks between polymer molecules and cure.
- an atom in the polymer for example, a hydrogen atom on a carbon atom adjacent to a functional crosslinking group
- a free radical is extracted by a free radical to generate a polymer radical, which combines with one another to form a crosslink between polymer molecules It forms and cures.
- the content of the crosslinkable group in the binder polymer is preferably 0.1 per gram of the binder polymer from the viewpoint of good sensitivity and good storage stability. It is preferably -10.0 mmol, more preferably 1.0-7.0 mmol, still more preferably 2.0-5.5 mmol.
- the binder polymer is shown below, but the present invention is not limited thereto.
- the numerical values shown in parallel with each repeating unit represent the mole percentage of the repeating unit.
- the numerical value added to the repeating unit of the side chain indicates the number of repeats of the repeating site.
- Me represents a methyl group
- Et represents an ethyl group
- Ph represents a phenyl group.
- the molecular weight of the binder polymer is 2,000 or more, preferably 5,000 or more, and more preferably 10,000 to 300,000, as weight average molecular weight (Mw) as polystyrene conversion value by GPC method. Further, in the present invention, the oligomer has a Mw of 800 or more and less than 2,000, and the polymer has a Mw of 2,000 or more.
- hydrophilic polymers such as polyacrylic acid and polyvinyl alcohol described in JP-A-2008-195018 can be used in combination. Also, lipophilic polymers and hydrophilic polymers can be used in combination.
- the binder polymer may be present in the composition as a polymer functioning as a binder for each component, or in the form of particles.
- the volume average primary particle size is preferably 10 to 1,000 nm, more preferably 20 to 300 nm, and still more preferably 30 to 120 nm.
- the volume average primary particle size can be obtained by taking an electron micrograph of the particle, measuring the total particle size of 5000 particles on the photograph, and calculating the arithmetic mean value.
- the particle diameter value of spherical particles having the same particle area as the particle area on the photograph is measured as the particle diameter (equivalent circle diameter).
- the method of measuring the volume average primary particle size is the same as for the particles other than the binder polymer present in the form of particles, unless otherwise specified.
- the binder polymer may be used alone or in combination of two or more.
- the binder polymer can be contained in any amount in the composition.
- the content of the binder polymer can be appropriately selected depending on the application of the composition of the present invention and the like, but it is preferably 1 to 90% by mass, more preferably 5 to 80% by mass in the total solid content of the composition.
- the composition of the present invention can contain an acid color former.
- the acid color former is a compound having a property of developing a color by accepting an electron accepting compound (for example, a proton such as an acid).
- an acid color developing agent a colorless compound which has a partial skeleton such as lactone, lactam, sultone, spiropyran, ester or amide, and which partially opens or cleaves the partial skeleton when contacted with an electron accepting compound preferable.
- acid-coloring agents examples include: 3,3-bis (4-dimethylaminophenyl) -6-dimethylaminophthalide (referred to as "crystal violet lactone"), 3,3-bis (4- Dimethylaminophenyl) phthalide, 3- (4-dimethylaminophenyl) -3- (4-diethylamino-2-methylphenyl) -6-dimethylaminophthalide, 3- (4-dimethylaminophenyl) -3- (1 , 2-Dimethylindol-3-yl) phthalide, 3- (4-dimethylaminophenyl) -3- (2-methylindol-3-yl) phthalide, 3,3-bis (1,2-dimethylindole-3) -Yl) -5-dimethylaminophthalide, 3,3-bis (1,2-dimethylindol-3-yl) -6-dimethylaminophthalide, 3,3-biphenyl (9-E
- the acid color former is preferably at least one compound selected from the group consisting of spiropyran compounds, spirooxazine compounds, spirolactone compounds and spirolactam compounds.
- the hue of the dye after color development is preferably green, blue or black from the viewpoint of visibility.
- the acid color former it is also possible to use a commercial item as the acid color former.
- ETAC RED 500, RED 520, CVL, S-205, BLACK 305, BLACK 400, BLACK 100, BLACK 500, H-7001, GREEN 300, NIRBLACK 78, BLUE 220, H-3035, BLUE 203, ATP, H-1046, H-2114 (more, Fukui Yamada Chemical Industry Co., Ltd., ORANGE-DCF, Vermilion-DCF, PINK-DCF, RED-DCF, BLMB, CVL, GREEN-DCF, TH-107 (above, Hodogaya Chemical Co., Ltd.), ODB, ODB-2, ODB-4, ODB-250, ODB-BlackXV, Blue-63, Blue-502, GN-169, GN-2, Green-118, Red-40, Red-8 (above, Yamamoto Kasei ) Co., Ltd.), crystal violet lactone (manufactured by Tokyo Chemicals Industry Co
- the acid color former may be used alone or in combination of two or more.
- the content of the acid color former is preferably 0.1 to 20% by mass, more preferably 1 to 15% by mass, and still more preferably 2 to 10% by mass in the total solid content of the composition of the present invention.
- the acid color former develops color when used in combination with an acid generator.
- the acid generator is a compound that generates an acid by electron transfer and / or energy transfer from an infrared absorber excited by infrared radiation.
- the generated acid reacts with the acid color former to form a color.
- As the acid to be generated sulfonic acid, hydrochloric acid, hexafluorophosphoric acid, tetrafluoroboric acid and the like are useful.
- Examples of the acid generator include onium salts such as iodonium salts, sulfonium salts, phosphonium salts, diazonium salts and azinium salts.
- onium salts such as iodonium salts, sulfonium salts, phosphonium salts, diazonium salts and azinium salts.
- onium salts such as iodonium salts, sulfonium salts, phosphonium salts, diazonium salts and azinium salts.
- onium salts such as iodonium salts, sulfonium salts, phosphonium salts, diazonium salts and azinium salts.
- benzyl sulfonates described in US Pat. Nos. 5,135,838 and 5,200,544.
- imido esters such as sulfonic acid esters and disulfone compounds described in JP-A-61-166544, JP-A-2003-328465, and the like.
- J. Org. C. S. Perkin II (1979) 156-162 Journal of Photopolymer Science and Technology (1995) 202-232
- JP-A-2000-66385, JP-A-2000-80068, JP-A-2008-195018 Compounds are also preferred.
- haloalkyl-substituted s-triazine compounds described in JP-A-7-27129 are also preferable.
- iodonium salts As the acid generator, iodonium salts, sulfonium salts and azinium salts are particularly preferred.
- the descriptions of the iodonium salts and sulfonium salts in the above-mentioned polymerization initiator can be incorporated.
- the acid generator can contain the organic anion according to the present invention as an anion.
- the acid generator corresponds to the specific compound according to the present invention.
- the acid generator may be used alone or in combination of two or more.
- the content of the acid generator is preferably 1 to 30% by mass, more preferably 3 to 20% by mass, and still more preferably 6 to 15% by mass, in the total solid content of the composition of the present invention.
- the composition of the present invention may contain a radical formation coagent.
- the radical forming aid contributes to the improvement of the printing durability of the lithographic printing plate prepared from the lithographic printing plate precursor.
- a radical formation adjuvant the following five types are mentioned, for example.
- Alkyl or arylate complex It is thought that a carbon-hetero bond is oxidatively cleaved to generate an active radical. Specifically, borate compounds and the like can be mentioned.
- Aminoacetic acid compound It is believed that oxidation breaks up the C—X bond on the carbon adjacent to nitrogen to generate an active radical.
- a hydrogen atom, a carboxy group, a trimethylsilyl group or a benzyl group is preferable.
- N-phenylglycines a phenyl group may have a substituent
- N-phenyliminodiacetic acid a phenyl group may have a substituent
- Be (Iii) Sulfur-containing compounds Those in which the nitrogen atom of the above-mentioned aminoacetic acid compound is replaced by a sulfur atom can generate an active radical by the same action. Specific examples thereof include phenylthioacetic acid (which may have a substituent on the phenyl group) and the like.
- Tin-containing compounds those in which the nitrogen atom of the above-mentioned aminoacetic acid compound is replaced by a tin atom can generate active radicals by the same action.
- Sulfinates Oxidation can generate active radicals. Specifically, sodium arylsulfine and the like can be mentioned.
- borate compounds are preferred.
- a tetraaryl borate compound or a monoalkyl triaryl borate compound is preferable, and from the viewpoint of compound stability, a tetraaryl borate compound is more preferable.
- a counter cation which a borate compound has an alkali metal ion or a tetraalkyl ammonium ion is preferable, and a sodium ion, a potassium ion, or a tetrabutyl ammonium ion is more preferable.
- X c + represents a monovalent cation, and is preferably an alkali metal ion or a tetraalkylammonium ion, and more preferably an alkali metal ion or a tetrabutylammonium ion.
- Bu represents an n-butyl group.
- the radical generation assistant may be used alone or in combination of two or more.
- the content of the radical formation aid is preferably 0.01 to 30% by mass, more preferably 0.05 to 25% by mass, and further preferably 0.1 to 20% by mass, based on the total solid content of the composition of the present invention. preferable.
- the composition of the present invention may contain polymer particles from the viewpoint of improving the on-press developability of the lithographic printing plate precursor.
- the polymer particles are preferably polymer particles that can convert the image recording layer to hydrophobic when heat, preferably heat generated by exposure, is applied.
- the polymer particles are at least one selected from heat fusible particles, heat reactive polymer particles, polymer particles having a polymerizable group, microcapsules containing a hydrophobic compound, and microgel (crosslinked polymer particles). Is preferred. Among them, polymer particles and microgels having a polymerizable group are preferable.
- thermoplastic polymer particles described in JP-A-9-123387, JP-A-9-131850, JP-A-9-171249, JP-A-9-171250, European Patent 931647, etc. are preferred. It can be mentioned.
- the polymer constituting the heat fusible particle include ethylene, styrene, vinyl chloride, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, vinylidene chloride, acrylonitrile, vinyl carbazole, polyalkylene structure And homopolymers or copolymers of monomers such as acrylates or methacrylates, or mixtures thereof.
- polystyrene, a copolymer containing styrene and acrylonitrile, and polymethyl methacrylate can be mentioned.
- the number average primary particle size of the heat fusible particles is preferably 0.01 to 2.0 ⁇ m.
- the thermally reactive polymer particles include polymer particles having a thermally reactive group.
- the polymer particles having a thermally reactive group form a hydrophobized region by crosslinking due to thermal reaction and functional group change at that time.
- the thermally reactive group in the polymer particle having a thermally reactive group may be a functional group which carries out any reaction as long as a chemical bond is formed, and a polymerizable group is preferred.
- a polymerizable group examples thereof include ethylenically unsaturated groups (for example, acryloyl group, methacryloyl group, vinyl group, allyl group etc.) which undergo radical polymerization reaction, cationically polymerizable groups (for example, vinyl group, vinyloxy group, epoxy group, oxetanyl group) Etc.), isocyanato group to perform addition reaction or a block thereof, epoxy group, vinyloxy group and functional group having active hydrogen atom (such as amino group, hydroxy group, carboxy group etc.) which is a reaction partner thereof, condensation reaction Preferred examples thereof include a carboxy group to be carried out and a hydroxy group or amino group which is a reaction partner, an acid anhydride which performs a ring-opening addition reaction, an amino group or
- microcapsules examples include those in which all or part of the components of the image recording layer are encapsulated in microcapsules, as described in JP-A-2001-277740 and JP-A-2001-277742.
- the components of the image recording layer can also be contained outside the microcapsules.
- a hydrophobic component is encapsulated in the microcapsule and a hydrophilic component is contained outside the microcapsule.
- the microgel can contain part of the components of the composition of the present invention on at least one of its interior and surface.
- a reactive microgel is obtained by having a radically polymerizable group on the surface is preferable from the viewpoint of image formation sensitivity and printing durability.
- the volume average particle size of the microcapsules or microgels is preferably 0.01 to 3.0 ⁇ m, more preferably 0.05 to 2.0 ⁇ m, and still more preferably 0.10 to 1.0 ⁇ m. Within this range, good resolution and stability over time can be obtained.
- the volume average particle size is measured by a light scattering method using a dynamic light scattering type particle size distribution measuring apparatus LB-500 (manufactured by Horiba, Ltd.).
- the content of the polymer particles is preferably 5 to 90% by mass in the total solid content of the composition of the present invention.
- the composition of the present invention may contain a chain transfer agent.
- the chain transfer agent when the composition of the present invention is applied to the image recording layer of a lithographic printing plate precursor, contributes to the improvement of the printing durability of a lithographic printing plate prepared from the lithographic printing plate precursor.
- the chain transfer agent is preferably a thiol compound, more preferably a thiol having a carbon number of 7 or more from the viewpoint of boiling point (poor volatility), and still more preferably a compound having a mercapto group on an aromatic ring (aromatic thiol compound).
- the thiol compound is preferably a monofunctional thiol compound.
- the chain transfer agent may be used alone or in combination of two or more.
- the content of the chain transfer agent is preferably 0.01 to 50% by mass, more preferably 0.05 to 40% by mass, and still more preferably 0.1 to 30% by mass in the total solid content of the composition of the present invention .
- Low molecular weight hydrophilic compound When the composition of the present invention is applied to the image recording layer of a lithographic printing plate precursor, the on-press development of the lithographic printing plate precursor without reducing the printing durability of the lithographic printing plate prepared from the lithographic printing plate precursor In order to improve the properties, low molecular weight hydrophilic compounds may be contained.
- the low molecular weight hydrophilic compound is preferably a compound having a molecular weight of less than 1,000, more preferably a compound having a molecular weight of less than 800, and still more preferably a compound having a molecular weight of less than 500.
- hydrophilic compounds for example, as water-soluble organic compounds, glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol and the like, ethers or ester derivatives thereof, glycerin, Polyols such as pentaerythritol, tris (2-hydroxyethyl) isocyanurate, organic amines such as triethanolamine, diethanolamine and monoethanolamine and salts thereof, organic sulfones such as alkyl sulfonic acid, toluene sulfonic acid and benzene sulfonic acid Acids and salts thereof, organic sulfamic acids such as alkyl sulfamic acids and salts thereof, organic sulfuric acids such as alkyl sulfuric acids and alkyl ether sulfuric acids and salts thereof, phenyl phosphonic acid Organic phosphonic acids and salts thereof, tartaric acid
- the low molecular weight hydrophilic compound is preferably at least one selected from polyols, organic sulfates, organic sulfonates and betaines.
- organic sulfonates include alkyl sulfonates such as sodium n-butyl sulfonate, sodium n-hexyl sulfonate, sodium 2-ethylhexyl sulfonate, sodium cyclohexyl sulfonate, sodium n-octyl sulfonate; , 8,11-Trioxapentadecane-1-sulfonic acid sodium, 5,8,11-trioxaheptadecane-1-sulfonic acid sodium, 13-ethyl-5,8,11-trioxaheptadecane-1-sulfone Alkyl sulfonates containing ethylene oxide chains such as sodium acid sodium and sodium 5,8,11,14-tetraoxatetracosan-1-sulphonate; sodium benzene sulphonate, sodium p-toluene sulphonate, p-hydroxy benzene sulphide
- Organic sulfates include sulfates of alkyl, alkenyl, alkynyl, aryl or heterocyclic monoethers of polyethylene oxide.
- the number of ethylene oxide units is preferably 1 to 4, and the salt is preferably a sodium salt, potassium salt or lithium salt. Specific examples thereof include the compounds described in paragraphs 0034 to 0038 of JP-A-2007-276454.
- Preferred betaines are compounds having 1 to 5 carbon atoms in the hydrocarbon substituent to the nitrogen atom, and specific examples thereof include trimethyl ammonium acetate, dimethyl propyl ammonium acetate, 3-hydroxy-4-trimethyl ammonium Obtilate, 4- (1-pyridinio) butyrate, 1-hydroxyethyl-1-imidazolioacetate, trimethylammonium methanesulfonate, dimethylpropylammonium methanesulfonate, 3-trimethylammonio-1-propanesulfonate, 3 And-(1-pyridinio) -1-propanesulfonate and the like.
- the low molecular weight hydrophilic compound has a small hydrophobic part structure and has little surface activity, so that dampening water penetrates the exposed area (image area) of the image recording layer to reduce the hydrophobicity and film strength of the image area. And the ink receptivity and the printing durability of the image recording layer can be well maintained.
- the low molecular weight hydrophilic compounds may be used alone or in combination of two or more.
- the content of the low molecular weight hydrophilic compound is preferably 0.5 to 20% by mass, more preferably 1 to 15% by mass, and still more preferably 2 to 10% by mass in the total solid content of the composition of the present invention.
- the ink receptivity of the lithographic printing plate prepared from the lithographic printing plate precursor (hereinafter, also simply referred to as "inking property")
- a sensitizing agent such as a phosphonium compound, a nitrogen-containing low molecular weight compound, or an ammonium group-containing polymer may be contained.
- these compounds function as a surface coating agent for the inorganic stratiform compound, and suppress the decrease in the ink resistance during printing by the inorganic stratiform compound. it can.
- a sensitizing agent it is preferable to use a phosphonium compound, a nitrogen-containing low molecular weight compound, and an ammonium group-containing polymer in combination, and to use a phosphonium compound, a quaternary ammonium salt, and an ammonium group-containing polymer in combination. Is more preferred.
- the nitrogen-containing low molecular weight compounds include amine salts and quaternary ammonium salts. Also, imidazolinium salts, benzimidazolinium salts, pyridinium salts, quinolinium salts can be mentioned. Among them, quaternary ammonium salts and pyridinium salts are preferred.
- the ammonium group-containing polymer may have an ammonium group in its structure, and is preferably a polymer containing 5 to 80 mol% of (meth) acrylate having an ammonium group in a side chain as a copolymerization component.
- Specific examples include the polymers described in paragraphs 0089 to 0105 of JP-A-2009-208458.
- the ammonium salt-containing polymer preferably has a reduced specific viscosity (unit: ml / g) value of 5 to 120, preferably 10 to 110, which is determined according to the measurement method described in JP-A 2009-208458. Are more preferred, and those in the range of 15 to 100 are particularly preferred.
- Mw weight average molecular weight
- the content of the sensitizing agent is preferably 0.01 to 30% by mass, more preferably 0.1 to 15% by mass, and still more preferably 1 to 10% by mass, in the total solid content of the composition of the present invention.
- the image recording layer of the lithographic printing plate precursor according to the invention can contain a dye having large absorption in the visible light region as a colorant for an image.
- a dye having large absorption in the visible light region As a colorant for an image.
- pigments such as phthalocyanine pigments, azo pigments, carbon black and titanium oxide can also be suitably used. It is preferable to contain a coloring agent, because the image area after image formation and the non-image area can be easily distinguished.
- the addition amount of the colorant is preferably 0.005 to 10% by mass with respect to the total solid content of the image recording layer.
- composition of the present invention can contain, as other components, surfactants, polymerization inhibitors, higher fatty acid derivatives, plasticizers, inorganic particles, inorganic layered compounds, and the like. Specifically, each component described in paragraphs [0114] to [0159] of JP-A-2008-284817 can be contained.
- the lithographic printing plate precursor of the invention has an image recording layer containing the composition of the invention on a support.
- an on-press development type lithographic printing plate precursor in which the features of the composition of the present invention are remarkably exhibited will be described as an example, but a development processing lithographic printing plate precursor for producing a lithographic printing plate by development processing Will also be described as appropriate.
- the image recording layer contains an infrared absorber, a polymerizable compound, a polymerization initiator, and at least one of a binder polymer and polymer particles.
- the image recording layer preferably further contains a radical generation aid and a chain transfer agent.
- the image recording layer contains an infrared absorber, heat fusible particles, and a binder polymer.
- the image recording layer may contain an acid color former.
- the specific compound according to the present invention can be used as a polymerization initiator and an infrared absorber.
- the specific compound according to the present invention can be used as an acid generator for the acid color former.
- Respective components such as an infrared absorber, a polymerizable compound, a polymerization initiator, a binder polymer, a polymer particle, a radical generation aid, a chain transfer agent, a thermally fusible particle and the content thereof contained in the image recording layer See the description in the composition of the present invention above.
- the image recording layer is prepared by dispersing or dissolving the necessary components described above in a solvent to prepare a coating solution, and the coating solution on a support It can form by apply
- a well-known solvent can be used as a solvent.
- a solvent may be used individually by 1 type, and may use 2 or more types together.
- the solid concentration in the coating solution is preferably about 1 to 50% by mass.
- the coating amount (solid content) of the image recording layer after coating and drying varies depending on the application, but from the viewpoint of obtaining good sensitivity and good film properties of the image recording layer, it is about 0.3 to 3.0 g / m 2. Is preferred.
- the lithographic printing plate precursor according to the invention preferably has a subbing layer (sometimes referred to as an intermediate layer) between the image recording layer and the support.
- the undercoat layer strengthens the adhesion between the support and the image recording layer in the exposed area and facilitates the peeling of the image recording layer from the support in the unexposed area. Contribute to improving In addition, in the case of infrared laser exposure, the undercoat layer functions as a heat insulating layer, which also has an effect of preventing a decrease in sensitivity due to heat generated by the exposure being diffused to the support.
- Examples of the compound used for the undercoat layer include polymers having an adsorptive group capable of adsorbing to the surface of the support and a hydrophilic group. In order to improve the adhesion to the image recording layer, polymers having an adsorptive group and a hydrophilic group, and further having a crosslinkable group are preferred.
- the compound used for the undercoat layer may be a low molecular weight compound or a polymer. The compounds used in the undercoat layer may be used as a mixture of two or more, if necessary.
- the compound used for the undercoat layer is a polymer
- a copolymer of a monomer having an adsorptive group, a monomer having a hydrophilic group and a monomer having a crosslinkable group is preferred.
- adsorptive groups capable of adsorbing to the surface of a support include phenolic hydroxy group, carboxy group, -PO 3 H 2 , -OPO 3 H 2 , -CONHSO 2- , -SO 2 NHSO 2- , -COCH 2 COCH 3 Is preferred.
- the hydrophilic group is preferably a sulfo group or a salt thereof, or a salt of a carboxy group.
- the polymer may have a crosslinkable group introduced by salt formation of a polar substituent of the polymer and a compound having a polar substituent and a substituent having a counter charge and a compound having an ethylenically unsaturated bond, or other than the above.
- Further monomers, preferably hydrophilic monomers, may be further copolymerized.
- the phosphorus compound which has a heavy bond reactive group is mentioned suitably.
- Crosslinkable groups (preferably, ethylenically unsaturated bond groups) described in JP 2005-238816, JP 2005-125749, JP 2006-239867, and JP 2006-215263, and a support Low molecular weight or high molecular weight compounds having a functional group that interacts with the surface and a hydrophilic group are also preferably used.
- More preferable examples include polymer polymers having an adsorptive group, a hydrophilic group and a crosslinkable group which can be adsorbed on the surface of a support as described in JP-A-2005-125749 and JP-A-2006-188038.
- the content of the ethylenically unsaturated bond group in the polymer used for the undercoat layer is preferably 0.1 to 10.0 mmol, more preferably 0.2 to 5.5 mmol, per 1 g of the polymer.
- the weight average molecular weight (Mw) of the polymer used for the undercoat layer is preferably 5,000 or more, and more preferably 10,000 to 300,000.
- the undercoat layer has a chelating agent, a secondary or tertiary amine, a polymerization inhibitor, an amino group or a functional group having a polymerization inhibiting ability and a support surface in order to prevent soiling over time.
- DABCO 1,4-diazabicyclo [2.2.2] octane
- 2,3,5,6-tetrahydroxy-p-quinone chloranil
- sulfophthalic acid hydroxy It may contain ethyl ethylenediamine triacetic acid, dihydroxyethyl ethylenediamine diacetic acid, hydroxyethyl imino diacetic acid, and the like.
- the subbing layer is applied in a known manner.
- the coating amount (solid content) of the undercoat layer is preferably 0.1 ⁇ 100mg / m 2, and more preferably 1 ⁇ 30mg / m 2.
- the lithographic printing plate precursor of the invention may have a protective layer (sometimes called an overcoat layer) on the image recording layer.
- the protective layer has a function of preventing the generation of a scratch in the image recording layer and a function of preventing ablation during high-intensity laser exposure, in addition to the function of suppressing the image formation inhibition reaction by oxygen blocking.
- the protective layer having such properties is described, for example, in US Pat. No. 3,458,311 and JP-B-55-49729.
- a water-soluble polymer or a water-insoluble polymer can be appropriately selected and used, and two or more types can be mixed and used as needed. it can.
- polyvinyl alcohol, modified polyvinyl alcohol, polyvinyl pyrrolidone, a water-soluble cellulose derivative, poly (meth) acrylonitrile and the like can be mentioned.
- the modified polyvinyl alcohol an acid modified polyvinyl alcohol having a carboxy group or a sulfo group is preferably used.
- modified polyvinyl alcohols described in JP-A-2005-250216 and JP-A-2006-259137 can be mentioned.
- the protective layer preferably contains an inorganic stratiform compound to enhance the oxygen barrier property.
- the inorganic stratiform compound is a particle having a thin tabular shape, and, for example, a mica group such as natural mica and synthetic mica, talc represented by the formula: 3MgO.4SiO.H 2 O, teniolite, montmorillonite, saponite, hekto Light, zirconium phosphate and the like can be mentioned.
- the inorganic layered compound preferably used is a mica compound.
- mica compound for example, a compound represented by the formula: A (B, C) 2-5 D 4 O 10 (OH, F, O) 2 (wherein A represents at least one selected from the group consisting of K, Na and Ca) And B and C are at least one element selected from the group consisting of Fe (II), Fe (III), Mn, Al, Mg and V, and D is Si or Al. is there. And micas such as natural micas and synthetic micas.
- natural micas include muscovite, soda mica, phlogopite, biotite and phlogopite.
- synthetic smectites are also useful.
- the bond between the layered crystal lattices is weak because the ion radius is small, and the layer swells significantly with water. In this state, shearing readily cleaves to form a stable sol in water. Swellable synthetic mica is strong in this tendency and 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 particle, and can be measured, for example, from a projection of the particle by a micrograph. The larger the aspect ratio, the greater the effect obtained.
- the average major axis of the particle diameter of the mica compound is preferably 0.3 to 20 ⁇ m, more preferably 0.5 to 10 ⁇ m, and particularly preferably 1 to 5 ⁇ m.
- the average thickness of the particles is preferably 0.1 ⁇ m or less, more preferably 0.05 ⁇ m or less, and particularly preferably 0.01 ⁇ m or less.
- the thickness is about 1 to 50 nm and the surface size (long diameter) is about 1 to 20 ⁇ m.
- the content of the inorganic stratiform compound is preferably 0 to 60% by mass, and more preferably 3 to 50% by mass, with respect to the total solid content of the protective layer. Even when using a plurality of types of inorganic stratiform compounds in combination, it is preferable that the total amount of the inorganic stratiform compounds has the above content. Within the above range, the oxygen barrier property is improved and good sensitivity can be obtained. In addition, it is possible to prevent the deterioration of the inking property.
- the protective layer may contain known additives such as a plasticizer for imparting flexibility, a surfactant for improving the coatability, and inorganic particles for controlling the slipperiness of the surface.
- the protective layer may contain the specific compound according to the present invention.
- the protective layer may contain the sensitizing agent described in the image recording layer.
- the protective layer is applied in a known manner.
- the coating amount of the protective layer (solid content) is preferably 0.01 ⁇ 10g / m 2, more preferably 0.02 ⁇ 3g / m 2, particularly preferably 0.02 ⁇ 1g / m 2.
- the support of the lithographic printing plate precursor according to the present invention can be appropriately selected from known lithographic printing plate precursors.
- the support is preferably an aluminum plate which has been subjected to surface roughening and anodized by a known method.
- the aluminum plate may further be subjected to micropore enlargement treatment or sealing treatment of the anodized film described in JP-A-2001-253181 and JP-A-2001-322365 as required, US Pat. No.
- the support is, if necessary, an organic polymer compound described in JP-A-5-45885, an alkoxy compound of silicon described in JP-A-6-35174, etc. on the side opposite to the image recording layer. And may have a back coat layer containing
- the method of preparing a lithographic printing plate of the present invention comprises the step of imagewise exposing the lithographic printing plate precursor of the present invention (exposure step), and the lithographic printing plate precursor after imagewise exposure on a printing press with printing ink and fountain solution It is preferable to include the step (on-press development step) of removing the unexposed area of the image recording layer according to at least one selected from the above.
- the step of imagewise exposing the lithographic printing plate precursor of the present invention exposure step
- the lithographic printing plate precursor after image exposure with a developer having a pH of 2 to 11
- Image exposure is preferably performed by a method of scanning exposure of digital data with an infrared laser or the like.
- the wavelength of the exposure light source is preferably 750 to 1,400 nm.
- a solid state laser and a semiconductor laser emitting infrared rays are preferable.
- the exposure mechanism may be any of an inner drum system, an outer drum system, a flat bed system, and the like.
- the exposure step can be performed by a plate setter or the like by a known method.
- the on-press development step is included, the lithographic printing plate precursor may be mounted on a printing press using a printing press equipped with an exposure device, and then exposure may be performed on the printing press.
- On-press development process In the on-press development step, at least one selected from the printing ink and the dampening water, preferably the printing ink and the dampening solution, on the printing press without subjecting the lithographic printing plate precursor after image exposure to any developing treatment.
- water is supplied to start printing (on-press development)
- the unexposed area of the lithographic printing plate precursor is removed at an early stage during printing, and the hydrophilic support surface is exposed accordingly and a non-image area is formed. Be done.
- Known printing inks and dampening solutions for lithographic printing are used as printing inks and dampening solutions.
- the printing ink or dampening solution may be supplied first to the surface of the lithographic printing plate precursor, the printing ink is the first to prevent the dampening solution from being contaminated by the removed image recording layer component. It is preferable to supply Thus, the lithographic printing plate precursor is developed on the offset printing press and used as it is for printing a large number of sheets.
- the method of preparing a lithographic printing plate of the present invention may include other known steps in addition to the above steps.
- Examples of other steps include a step of confirming the position and orientation of the lithographic printing plate precursor before each step, and a confirmation step of confirming a printed image after the on-press development step.
- the lithographic printing plate precursor of the present invention can also produce a lithographic printing plate by development processing using a developer by appropriately selecting a binder polymer and the like which are constituents of the image recording layer.
- the development processing using a developing solution is an embodiment using a high pH developing solution having a pH of 14 or less containing an alkaline agent (also referred to as alkaline development processing), and at least selected from the group consisting of a surfactant and a water-soluble polymer compound.
- This also includes an embodiment (also referred to as simplified development) that uses a developer having a pH of 2 to 11 and may contain one type of compound.
- the protective layer is removed by a pre-water-washing step, then alkali development is performed, the alkali is washed away by water in a post-water-washing step, gum solution treatment is performed, and drying is performed Drying is performed.
- the simple development process when the protective layer is provided, the protective layer is simultaneously removed, so that the pre-water washing step can be omitted.
- the development and the gum solution processing step can be simultaneously performed by containing a water-soluble polymer compound in the developer, if necessary.
- the post-water washing step is not particularly required, and the drying step can be carried out after the development and gum solution treatment are carried out in the one-component one-step process. Therefore, as a development process using a developing solution, a method of preparing a lithographic printing plate including a process of developing the planographic printing plate precursor after image exposure with a developing solution having a pH of 2 to 11 is preferable. It is preferable to dry after removing an excess developing solution using a squeeze roller after development processing.
- development treatment step of the method of preparing a lithographic printing plate according to the present invention it is preferable to carry out development treatment and gum solution treatment in one step for one solution.
- development and gum solution treatment in one solution it is not necessary to carry out development treatment and gum solution treatment as separate steps, but to make the developer contain a water-soluble polymer compound and use one solution. It means that development processing and gum solution processing are performed in one step.
- the development process can be suitably carried out by an automatic development processor equipped with a developer supply means and a rubbing member.
- an automatic development processor using a rotating brush roll as the rubbing member. Two or more rotating brush rolls are preferable.
- the automatic development processor comprises means for removing excess developer such as a squeeze roller after the development processing means, and drying means such as a hot air device.
- the automatic development processor may be provided with preheating means for heat-processing the lithographic printing plate precursor after image exposure, prior to the development processing means. Processing with such an automatic development processor is advantageous in that it is released from the correspondence with the development residue derived from the protective layer / photosensitive layer which occurs in the case of so-called on-press development processing.
- a developing processing method for example, a method in which an aqueous solution is contained in a sponge or cotton wool, processing while rubbing the entire plate surface, and drying after processing is preferable.
- a method of dipping the lithographic printing plate precursor in a vat or a deep tank containing an aqueous solution for about 60 seconds and agitating, and then rubbing while rubbing with absorbent cotton or a sponge is preferably used.
- an apparatus having a simplified structure and a simplified process be used for the development processing.
- the protective layer is removed by a pre-water washing step, followed by development with a high pH alkaline developer, after which the alkali is removed in a post-water washing step, gum treatment is performed in the gumming step, and drying step To dry.
- development and gumming can be performed simultaneously with one solution. Therefore, it is possible to omit the post-water washing step and the gum treatment step, and it is preferable to carry out the drying step as necessary after performing development and gumming (gum solution treatment) with one solution.
- after developing and gumming it is preferable to dry after removing an excess developing solution using a squeeze roller.
- the method of immersing in a developing solution once may be sufficient, and the method of immersing 2 times or more may be sufficient.
- the method of immersing in the developer solution once or twice is preferable.
- the exposed lithographic printing plate precursor may be dipped in a developer tank containing the developer, or the developer may be sprayed from a spray or the like onto the plate surface of the exposed lithographic printing plate precursor.
- the same developer, or a developer (fatigue solution) in which the components of the image recording layer are dissolved or dispersed by the developing process and the developer are used twice.
- development treatment with one solution one solution treatment
- a rubbing member such as a brush
- a rubbing member such as a brush
- the exposed lithographic printing plate precursor is dipped in a developer and rubbed with a brush, for example, at a temperature of preferably 0 ° C. to 60 ° C., more preferably 15 ° C. to 40 ° C.
- the treatment liquid charged in the external tank can be pumped up, sprayed from a spray nozzle, and rubbed with a brush.
- the developer charged in an external tank is pumped up and sprayed from a spray nozzle and rubbed with a brush
- the developer can be sprayed again from a spray nozzle and rubbed with a brush.
- it is preferable to recover the processing ability using a replenisher or a fresh developer because the developer becomes fatigued due to the increase of the processing amount.
- a gum coater and an automatic developing machine which are conventionally known for a PS plate (presensitized plate) and a CTP (computer to plate) can also be used.
- an automatic developing machine for example, a method in which a developer charged in a developer tank or a developer charged in an external tank is pumped up and treated by spraying from a spray nozzle, or in a tank filled with developer. Either a method in which the printing plate is conveyed by immersion in a submerged guide roll or the like for processing can be applied, or a so-called disposable processing method in which a substantially unused developer can be supplied and processed only for each plate can be applied. .
- a rubbing mechanism by a brush, molton, or the like is more preferable.
- a commercially available automatic processor (Clean Out Unit C85 / C125, Clean-Out Unit + C85 / 120, FCF 85 V, FCF 125 V, FCF News (manufactured by Glunz & Jensen), Azura CX85, Azura CX125, Azura CX150 (AGFA GRAPHICS) Company company, Inc.), or an apparatus in which a laser exposure unit and an automatic processor unit are integrated.
- the pH of the developer is preferably 2 to 11, more preferably 5 to 9, and still more preferably 7 to 9. From the viewpoint of developability and dispersibility of the image recording layer, it is more advantageous to set the pH value higher, but it is more effective to set the pH value lower for printability, particularly for suppression of stains. is there.
- pH is a value measured at 25 ° C. using a pH meter (model number: HM-31, manufactured by Toa DKK).
- the developer may contain a surfactant such as an anionic surfactant, a nonionic surfactant, a cationic surfactant, or an amphoteric surfactant.
- the developer preferably contains at least one selected from the group consisting of anionic surfactants and amphoteric surfactants, from the viewpoint of blanching. Further, the developer preferably contains a nonionic surfactant, and contains a nonionic surfactant and at least one selected from the group consisting of an anionic surfactant and an amphoteric surfactant. Is more preferred.
- R 1 represents an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group or an aryl group which may have a substituent.
- alkyl group for example, an alkyl group having 1 to 20 carbon atoms is preferable, and specifically, methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, Preferred examples include octyl group, decyl group, dodecyl group, hexadecyl group and stearyl group.
- the cycloalkyl group may be monocyclic or polycyclic.
- the monocyclic type is preferably a monocyclic cycloalkyl group having a carbon number of 3 to 8, and more preferably a cyclopropyl group, a cyclopentyl group, a cyclohexyl group or a cyclooctyl group.
- Preferred examples of the polycyclic group include an adamantyl group, a norbornyl group, an isoboronyl group, a camphanyl group, a dicyclopentyl group, an ⁇ -pinel group and a tricyclodecanyl group.
- the alkenyl group is preferably, for example, an alkenyl group having a carbon number of 2 to 20, and specific examples thereof preferably include a vinyl group, an allyl group, a butenyl group and a cyclohexenyl group.
- the aralkyl group is preferably, for example, an aralkyl group having a carbon number of 7 to 12, and specific examples thereof preferably include a benzyl group, a phenethyl group and a naphthylmethyl group.
- the aryl group is preferably, for example, an aryl group having a carbon number of 6 to 15, and specific examples thereof include a phenyl group, a tolyl group, a dimethylphenyl group, a 2,4,6-trimethylphenyl group, a naphthyl group and an anthryl group. Groups and 9,10-dimethoxyanthryl group etc. can be preferably mentioned.
- a monovalent nonmetal atomic group other than a hydrogen atom is used, and preferred examples include a halogen atom (F, Cl, Br or I), a hydroxy group, an alkoxy group, an aryloxy group, an acyl group, Amide groups, ester groups, acyloxy groups, carboxy groups, carboxylic acid anion groups, sulfonic acid anion groups and the like can be mentioned.
- a halogen atom F, Cl, Br or I
- a hydroxy group an alkoxy group
- an aryloxy group an acyl group
- Amide groups, ester groups, acyloxy groups, carboxy groups, carboxylic acid anion groups, sulfonic acid anion groups and the like can be mentioned.
- alkoxy group in the substituent examples include methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butyloxy group, pentyloxy group, hexyloxy group, dodecyloxy group, stearyloxy group, methoxyethoxy group, poly ( Those having preferably 1 to 40 carbon atoms, more preferably 1 to 20 carbon atoms, such as ethyleneoxy) group, poly (propyleneoxy) group and the like can be mentioned.
- the aryloxy group has 6 to 18 carbon atoms, such as phenoxy, tolyloxy, xylyloxy, mesityloxy, cumenyloxy, methoxyphenyloxy, ethoxyphenyloxy, chlorophenyloxy, bromophenyloxy, naphthyloxy and the like
- the ones of Examples of the acyl group include those having 2 to 24 carbon atoms such as acetyl group, propanoyl group, butanoyl group, benzoyl group and naphthoyl group.
- the amide group examples include those having 2 to 24 carbon atoms such as an acetamide group, a propionic acid amide group, a dodecanoic acid amide group, a palmitic acid amide group, a stearic acid amide group, a benzoic acid amide group and a naphthoic acid amide group.
- the acyloxy group those having 2 to 20 carbon atoms such as acetoxy group, propanoyloxy group, benzoyloxy group, naphthoyloxy group and the like can be mentioned.
- ester group examples include those having 1 to 24 carbon atoms such as methyl ester group, ethyl ester group, propyl ester group, hexyl ester group, octyl ester group, dodecyl ester group and stearyl ester group.
- the substituent may consist of a combination of two or more of the above substituents.
- X 1 represents a sulfonate group, a sulfate monoester base, a carboxylate group or a phosphate group.
- Y 1 is a single bond, -C n H 2n- , -C n -m H 2 (n-m) OC m H 2m- , -O- (CH 2 CH 2 O) n- , -O- (CH 2 CH 2 CH 2 O) n- , -CO-NH-, or a divalent linking group consisting of a combination of two or more of these, and n 1 1 and n m m 0 0 are satisfied.
- a compound represented by the following formula (IA) or the formula (IB) is preferable from the viewpoint of scratch resistance.
- each of R A1 to R A10 independently represents a hydrogen atom or an alkyl group
- nA represents an integer of 1 to 3
- X A1 and X A2 each represent Each independently represents a sulfonate group, a sulfate monoester base, a carboxylate group or a phosphate group
- Y A1 and Y A2 are each independently a single bond, —CnH 2n —, —C n-m H 2 (n-m ) OC m H 2 m- , -O- (CH 2 CH 2 O) n- , -O- (CH 2 CH 2 CH 2 O) n- , -CO-NH-, or a combination of two or more of them
- the total carbon number of R A1 to R A5 and Y 1A , or R A6 to R A10 and Y A2 in the compound represented by the above formula (I-A) or formula (I-B) is 25 or less Is preferable, and 4 to 20 is more preferable.
- the structure of the alkyl group described above may be linear or branched.
- X A1 and X A2 in the compound represented by the formula (IA) or the formula (IB) are preferably a sulfonate group or a carboxylate group.
- the salt structure of X A1 and X A2 is preferably an alkali metal salt, because the solubility in an aqueous solvent is particularly good. Among them, sodium salts or potassium salts are particularly preferred.
- JP-A-2007-206348 As the compound represented by the above formula (IA) or formula (IB), the description in paragraphs [0019] to [0037] of JP-A-2007-206348 can be referred to.
- anionic surfactant compounds described in paragraphs 0023 to 0028 of JP-A-2006-65321 can also be suitably used.
- amphoteric surfactant to be used in the developer is not particularly limited, and amine oxides such as alkyldimethylamine oxide, alkylbetaines, fatty acid amidopropyl betaines, betaines such as alkylimidazole, amino acids such as sodium alkylamino fatty acid It can be mentioned.
- alkyldimethylamine oxide which may have a substituent alkyl carboxy betaine which may have a substituent
- alkyl sulfo betaine which may have a substituent
- Specific examples thereof include a compound represented by the formula (2) in paragraph 0256 of JP-A-2008-203359, a formula (I), a formula (II) and a formula (II) in paragraph 0028 of JP-A-2008-276166.
- Examples thereof include compounds represented by VI) and compounds described in paragraphs 0022 to 0029 of JP-A-2009-47927.
- a compound represented by the following general formula (1) or a compound represented by the general formula (2) is preferable.
- R 1 and R 11 each independently represent an alkyl group having a carbon number of 8 to 20 or a linking group having a total carbon number of 8 to 20.
- R 2 , R 3 , R 12 and R 13 independently represents a hydrogen atom, an alkyl group or a group containing an ethylene oxide group.
- R 4 and R 14 each independently represent a single bond or an alkylene group.
- two groups among R 1 , R 2 , R 3 and R 4 may be bonded to each other to form a ring structure, and two groups among R 11 , R 12 , R 13 and R 14 may be each other It may combine to form a ring structure.
- the total carbon number of R 1 to R 4 or R 11 to R 14 is preferably 10 to 40, more preferably 12 to 30.
- the alkyl group having a linking group represented by R 1 or R 11 represents a structure having a linking group between the alkyl groups. That is, when there is one linking group, it can be represented by "-alkylene group-linking group-alkyl group".
- the linking group includes an ester bond, a carbonyl bond and an amide bond. Although two or more linking groups may be present, one linking group is preferred, and an amide bond is particularly preferred.
- the total carbon number of the alkylene group to be bonded to the linking group is preferably 1 to 5.
- the alkylene group may be linear or branched, but a linear alkylene group is preferred.
- the alkyl group bonded to the linking group preferably has 3 to 19 carbon atoms, and may be linear or branched, but is preferably linear alkyl.
- R 2 or R 12 is an alkyl group
- the number of carbon atoms is preferably 1 to 5, and particularly preferably 1 to 3. It may be either linear or branched, but is preferably a linear alkyl group.
- R 3 or R 13 is an alkyl group
- the number of carbon atoms is preferably 1 to 5, particularly preferably 1 to 3. It may be either linear or branched, but is preferably a linear alkyl group.
- a group containing ethylene oxide represented by R 3 or R 13 a group represented by —R a (CH 2 CH 2 O) n R b can be mentioned.
- R a represents a single bond, an oxygen atom or a divalent organic group (preferably having a carbon number of 10 or less)
- R b represents a hydrogen atom or an organic group (preferably having a carbon number of 10 or less)
- n is 1 Represents an integer of ⁇ 10.
- R 4 and R 14 are an alkylene group
- the number of carbon atoms is preferably 1 to 5, and particularly preferably 1 to 3. It may be either linear or branched, but is preferably a linear alkylene group.
- the compound represented by the general formula (1) or the compound represented by the general formula (2) preferably has an amide bond, and more preferably has an amide bond as a linking group of R 1 or R 11 . Representative examples of the compound represented by the general formula (1) or the compound represented by the general formula (2) are shown below, but the present invention is not limited thereto.
- the compounds represented by the general formula (1) or (2) can be synthesized according to known methods. Moreover, it is also possible to use what is marketed. Examples of commercially available products of the compound represented by the general formula (1) include Softazoline LPB manufactured by Kawaken Fine Chemical Co., Ltd., Softazoline LPB-R, Vista MAP, Takesurf C-157L manufactured by Takemoto Yushi Co., and the like. Examples of the compound represented by the general formula (2) include softazoline LAO manufactured by Kawaken Fine Chemicals Co., Ltd., and Amogen AOL manufactured by Daiichi Kogyo Seiyaku Co., Ltd. The amphoteric surfactant may be used alone in the developer, or may be used in combination of two or more.
- nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene polystyryl phenyl ether, glycerin fatty acid partial esters, sorbitan fatty acid partial esters, pentaerythritol fatty acid partial esters, Propylene glycol mono fatty acid ester, sucrose fatty acid partial ester, polyoxyethylene sorbitan fatty acid partial ester, polyoxyethylene sorbitol fatty acid partial ester, polyethylene glycol fatty acid ester, polyglycerin fatty acid partial ester, polyoxyethylene glycerin fatty acid partial ester , Polyoxyethylene diglycerins, fatty acid diethanolamides, N, N-bis-2-hydroxyalkylamine , Polyoxyethylene alkylamine, triethanolamine fatty acid esters, trialkylamine oxides, polyoxyethylene alkyl phenyl ethers, polyoxyethylene - polyoxypropylene block
- the nonionic aromatic ether surfactant represented by the following formula (N1) is particularly preferable as the nonionic surfactant.
- X N represents an aromatic group which may have a substituent
- Y N represents a single bond or an alkylene group having 1 to 10 carbon atoms
- a 1 and A 2 are groups different from each other
- nB and mB each independently represent an integer of 0 to 100, provided that nB and mB simultaneously represent one of -CH 2 CH 2 O- or -CH 2 CH (CH 3 ) O- If non-zero and either nB or mB is zero, then nB and mB are not one.
- examples of the aromatic group of X N include a phenyl group, a naphthyl group and an anthranyl group. These aromatic groups may have a substituent.
- the substituent includes an organic group having 1 to 100 carbon atoms. In the formula, when both A and B are present, it may be a random or block copolymer.
- organic group having 1 to 100 carbon atoms include an aliphatic hydrocarbon group which may be saturated or unsaturated and may be linear or branched, an aromatic hydrocarbon group such as an alkyl group, an alkenyl group or an alkynyl group. , Aryl groups, aralkyl groups, etc.
- the cationic surfactant is not particularly limited, and conventionally known ones can be used.
- alkylamine salts, quaternary ammonium salts, alkylimidazolinium salts, polyoxyethylene alkylamine salts, polyethylene polyamine derivatives and the like can be mentioned.
- the surfactant may be used alone or in combination of two or more.
- the content of the surfactant is preferably 1% by mass to 25% by mass, more preferably 2% by mass to 20% by mass, still more preferably 3% by mass to 15% by mass, with respect to the total mass of the developer. % To 10% by weight is particularly preferred.
- the scratch resistance is excellent, the dispersibility of development residue is excellent, and the ink receptivity of the obtained lithographic printing plate is excellent.
- the developer may contain a water-soluble polymer from the viewpoint of adjusting the viscosity of the developer and protecting the plate surface of the obtained lithographic printing plate.
- water-soluble polymers include soybean polysaccharides, modified starches, gum arabic, dextrin, fibrin derivatives (eg, carboxymethyl cellulose, carboxyethyl cellulose, methyl cellulose etc.) and modified products thereof, pullulan, polyvinyl alcohol and derivatives thereof, polyvinyl pyrrolidone, Water-soluble polymer compounds such as polyacrylamide and acrylamide copolymer, vinyl methyl ether / maleic anhydride copolymer, vinyl acetate / maleic anhydride copolymer, styrene / maleic anhydride copolymer, etc. can be contained .
- soybean polysaccharide conventionally known ones can be used.
- Soya Five manufactured by Fuji Oil Co., Ltd.
- various grades can be used.
- those which can be preferably used are those in which the viscosity of the 10% by mass aqueous solution is in the range of 10 mPa ⁇ s to 100 mPa ⁇ s.
- the starch represented by following formula (III) is preferable.
- any starch such as corn, potato, tapioca, rice, wheat and the like can be used.
- the modification of these starches can be performed by a method of decomposing in the range of 5 to 30 glucose residues per molecule with an acid or enzyme or the like and further adding oxypropylene in an alkali.
- the degree of etherification (degree of substitution) is in the range of 0.05 to 1.2 per glucose unit, n represents an integer of 3 to 30, and m represents an integer of 1 to 3.
- water-soluble polymer compounds particularly preferred are soybean polysaccharides, modified starches, gum arabic, dextrin, carboxymethylcellulose, polyvinyl alcohol and the like.
- the developer preferably contains no water-soluble polymer compound, or the content of the water-soluble polymer compound is preferably more than 0% by mass and not more than 1% by mass with respect to the total mass of the developer, and water-soluble Content of the water-soluble polymer compound is preferably more than 0% by mass and 0.1% by mass or less with respect to the total mass of the developer, and the water-soluble high content is high It is more preferable that the content of the water-soluble polymer compound does not contain a molecular compound or the content of the water-soluble polymer compound is more than 0% by mass and 0.05% by mass or less with respect to the total mass of the developer. It is particularly preferred not to contain The viscosity of a developing solution is moderate as it is the said aspect, and it can suppress that development debris etc. accumulate on the roller member of an automatic developing machine.
- the developing solution used in the present invention may contain, in addition to the above, a wetting agent, a preservative, a chelating compound, an antifoaming agent, an organic acid, an organic solvent, an inorganic acid, an inorganic salt and the like.
- ethylene glycol, propylene glycol, triethylene glycol, butylene glycol, hexylene glycol, diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, diglycerin and the like are suitably used.
- the wetting agents may be used alone or in combination of two or more.
- the content of the wetting agent is preferably 0.1% by mass to 5% by mass with respect to the total mass of the developer.
- the amount of the preservative to be added is an amount that exerts a stable effect on bacteria, mold, yeast and the like, and varies depending on the type of bacteria, mold and yeast, but is 0. 0 to the total mass of the developer.
- the range of 01% by mass to 4% by mass is preferable.
- salts of organic amines are also effective.
- the chelating agent is preferably one that is stably present in the treatment liquid composition and does not inhibit printability.
- the content of the chelating agent is preferably 0.001% by mass to 1.0% by mass with respect to the total mass of the developer.
- the antifoaming agent a general silicone-based self-emulsification type, an emulsification type, or a compound having a nonionic HLB (Hydrophilic-Lipophilic Balance) of 5 or less can be used. Silicone antifoams are preferred. In addition, silicone type surfactant shall be regarded as an antifoamer.
- the content of the antifoaming agent is preferably in the range of 0.001% by mass to 1.0% by mass with respect to the total mass of the developer.
- organic acid examples include citric acid, acetic acid, oxalic acid, malonic acid, salicylic acid, caprylic acid, tartaric acid, malic acid, lactic acid, levulinic acid, p-toluenesulfonic acid, xylenesulfonic acid, phytic acid, organic phosphonic acid and the like .
- the organic acids can also be used in the form of their alkali metal salts or ammonium salts.
- the content of the organic acid is preferably 0.01% by mass to 0.5% by mass with respect to the total mass of the developer.
- organic solvent for example, aliphatic hydrocarbons (hexane, heptane, “Isopar E, H, G” (manufactured by Esso Chemical Co., Ltd.), etc.), aromatic hydrocarbons (toluene, xylene, etc.), halogenated Examples thereof include hydrocarbons (methylene dichloride, ethylene dichloride, trichlene, monochlorobenzene etc.), polar solvents and the like.
- aliphatic hydrocarbons hexane, heptane, “Isopar E, H, G” (manufactured by Esso Chemical Co., Ltd.), etc.
- aromatic hydrocarbons toluene, xylene, etc.
- halogenated examples thereof include hydrocarbons (methylene dichloride, ethylene dichloride, trichlene, monochlorobenzene etc.), polar solvents and the like.
- alcohols methanol, ethanol, propanol, isopropanol, benzyl alcohol, ethylene glycol monomethyl ether, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether Propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol etc.) , Tons (acetone, methyl ethyl ketone, ethyl butyl ketone, methyl isobutyl ketone, cyclohexanone etc.), esters (ethyl acetate, propyl acetate, propyl
- the above organic solvent is insoluble in water, it can be used by solubilizing it in water using a surfactant etc.
- the developer contains an organic solvent, it is safe and flammable From the viewpoint, the concentration of the solvent in the developer is preferably less than 40% by mass.
- the inorganic acid and inorganic salt phosphoric acid, metaphosphoric acid, ammonium monophosphate, ammonium diphosphate, sodium monophosphate, sodium diphosphate, potassium monophosphate, potassium diphosphate, Sodium tripolyphosphate, potassium pyrophosphate, sodium hexametaphosphate, magnesium nitrate, sodium nitrate, potassium nitrate, ammonium nitrate, sodium sulfate, potassium sulfate, potassium sulfate, ammonium sulfate, sodium sulfite, ammonium sulfite, sodium hydrogensulfate, nickel sulfate and the like can be mentioned.
- the content of the inorganic salt is preferably 0.01% by mass to 0.5% by mass with respect to the total mass of the developer.
- the developer is prepared, as required, by dissolving or dispersing the above-mentioned components in water.
- the solid content concentration of the developer is preferably 2% by mass to 25% by mass.
- As a developing solution it is possible to prepare a concentrated solution and dilute it with water before use.
- the developer is preferably an aqueous developer.
- the developer preferably contains an alcohol compound from the viewpoint of the dispersibility of the development residue.
- an alcohol compound methanol, ethanol, propanol, isopropanol, benzyl alcohol and the like can be mentioned. Among them, benzyl alcohol is preferred.
- the content of the alcohol compound is preferably 0.01 to 5% by mass, more preferably 0.1 to 2% by mass, and more preferably 0.2 to 1% with respect to the total mass of the developer from the viewpoint of the dispersibility of the development residues. % By weight is particularly preferred.
- molecular weights are weight average molecular weights (Mw) in terms of polystyrene according to gel permeation chromatography (GPC) method, except for those specified specially, and the ratio of repeating units is molar percentage.
- “part” and “%” mean “mass part” and “mass%” unless there is particular notice.
- Me represents a methyl group.
- the above reaction solution was dropped into a 12 L stainless beaker to which 2700 g of distilled water and 300 g of methanol were added, and the mixture was stirred for 30 minutes after completion of the dropping.
- the precipitated solid was collected by filtration and washed with 2 L of distilled water, 5 L of an acetone / distilled water mixed solution (volume ratio 2/3), and further 5 L of an ethyl acetate / hexane mixed solution (volume ratio 1/3).
- the obtained solid was dried for 48 hours with a blower dryer set at 50 ° C. to obtain 358.0 g (0.30 mol) of Compound 1.
- the structure of the obtained compound 1 was identified by NMR. The identification results are shown below.
- ⁇ Preparation of support> In order to remove rolling oil on the surface of an aluminum plate (material JIS A 1050) with a thickness of 0.3 mm, a degreasing treatment was performed for 30 seconds at 50 ° C. using a 10 mass% sodium aluminate aqueous solution. Thereafter, the surface of the aluminum plate was grained using three bundle-planted nylon brushes having a diameter of 0.3 mm and a pumice-water suspension (specific gravity: 1.1 g / cm 3 ) having a median diameter of 25 ⁇ m, and thoroughly washed with water. The aluminum plate was etched by immersing it in a 25% by mass aqueous sodium hydroxide solution at 45 ° C.
- the etching amount of the grained surface was about 3 g / m 2 .
- the electrolytic solution was a 1 mass% nitric acid aqueous solution (containing 0.5 mass% of aluminum ion), and the liquid temperature was 50 ° C.
- the AC power supply waveform is electrochemically roughened with a carbon electrode as a counter electrode, using a trapezoidal rectangular wave AC with a time TP of 0.8 msec and a duty ratio of 1: 1 for the current value to reach a peak from zero Did. Ferrite was used for the auxiliary anode.
- the current density was 30 A / dm 2 at the peak value of the current, and 5% of the current flowing from the power supply was diverted to the auxiliary anode.
- the amount of electricity in nitric acid electrolysis was 175 C / dm 2 when the aluminum plate was an anode. After that, it was rinsed with a spray.
- nitric acid electrolysis is carried out using a 0.5 mass% aqueous solution of hydrochloric acid (containing 0.5 mass% of aluminum ion) and an electrolytic solution with a liquid temperature of 50 ° C. under the condition that the aluminum plate has an electric quantity of 50 C / dm 2 at the anode
- Electrochemical roughening treatment was carried out in the same manner as in the above, followed by washing with spray.
- using a 15% by weight aqueous solution of sulfuric acid (containing 0.5% by weight of aluminum ion) as an electrolytic solution form a direct current anodic oxide film of 2.5 g / m 2 at a current density of 15 A / dm 2 It dried and the support body A was produced.
- the average pore diameter (surface average pore diameter) in the surface layer of the anodized film was 10 nm.
- the measurement of the pore diameter in the surface layer of the anodized film uses an ultra-high resolution SEM (S-900 manufactured by Hitachi, Ltd.), and uses a deposition process or the like to impart conductivity at a relatively low acceleration voltage of 12 V.
- the surface was observed at a magnification of 150,000 times without application, and 50 pores were randomly extracted to obtain an average value.
- the standard deviation error was less than ⁇ 10%.
- support A was subjected to a silicate treatment at 60 ° C. for 10 seconds using a 2.5 mass% aqueous solution of sodium silicate No. 3 for 10 seconds, and washed to prepare support B. .
- the adhesion amount of Si was 10 mg / m 2 .
- the center line average roughness (Ra) of the support B was measured using a needle with a diameter of 2 ⁇ m and found to be 0.51 ⁇ m.
- a support C was produced in the same manner as the support A, except that, in the preparation of the support A, the electrolytic solution for forming the direct current anodic oxide film was changed to a 22% by mass aqueous phosphoric acid solution. It was 25 nm when the average pore diameter (surface average pore diameter) in the surface layer of the anodic oxide film was measured by the same method as the above.
- the support C is subjected to a silicate treatment at 60 ° C. for 10 seconds using a 2.5% by weight aqueous solution of sodium silicate No. 3 at 60 ° C. Made.
- the adhesion amount of Si was 10 mg / m 2 .
- the center line average roughness (Ra) of the support D was measured using a needle with a diameter of 2 ⁇ m and found to be 0.52 ⁇ m.
- undercoat layer coating solution (1) having the following composition was applied onto the support A so that the dry coating amount would be 20 mg / m 2 to form an undercoat layer.
- reaction solution was returned to room temperature (25 ° C., hereinafter the same), and then 175 parts of 30% by mass aqueous sodium hydroxide solution was added to adjust the pH to 8.3. Next, 0.152 parts of 4-OH-TEMPO was added, and the temperature was raised to 53.degree. 66.0 parts of methacrylic anhydride were added and stirred at 53 ° C. for 3 hours. After returning to room temperature, the reaction solution was transferred to a stainless beaker, and 1,800 parts of MTBE were added. After vigorously stirring, the mixture was allowed to stand and the upper layer was discarded.
- Blemmer PME 4000 methoxy polyethylene glycol methacrylate (the number of repeating oxyethylene units: 90)
- VA-046B 2,2'-azobis [2- (2-imidazolin-2-yl) propane] disulfate dihydrate
- An image recording layer coating solution (1) having the following composition was bar-coated on the undercoat layer, and oven-dried at 100 ° C. for 60 seconds to form an image recording layer having a dry coating amount of 1.0 g / m 2 .
- the image recording layer coating solution (1) was prepared by mixing and stirring the following photosensitive solution (1) and microgel solution immediately before coating.
- Microgel solution > ⁇ Microgel (1): 2.640 g Distilled water: 2.425 g
- the structures of the infrared ray absorber (D-1), the binder polymer (1), and the fluorinated surfactant (1) used in the photosensitive solution (1) are shown below.
- the numbers at the lower right of the parentheses of each constituent unit represent a molar ratio.
- microgel (1) used for the said microgel liquid is shown below.
- ⁇ Preparation of Polyvalent Isocyanate Compound (1)> A suspension of 17.78 g (80 mmol) of isophorone diisocyanate and 7.35 g (20 mmol) of the following polyhydric phenol compound (1) in ethyl acetate (25.31 g) was added with bismuth tris (2-ethylhexanoate) (neostan U). -600, 43 mg of Nitto Kasei Co., Ltd. was added and stirred. When the exotherm had subsided, the reaction temperature was set to 50 ° C., and stirring was performed for 3 hours to obtain an ethyl acetate solution (50% by mass) of the polyvalent isocyanate compound (1).
- the exposed lithographic printing plate precursor was mounted on a plate cylinder of a printing machine LITHRONE 26 manufactured by Komori Corporation without development processing.
- Ecoline 2 Fluji Film Co., Ltd. product
- tap water 2/98 (volume ratio) dampening water and Values-G (N) ink ink (DIC Graphics Co., Ltd. product), LITHRONE 26
- the dampening water and the ink were supplied by the standard automatic printing start method, and 100 sheets were printed on Tobishi Art Paper (76.5 kg) (manufactured by Mitsubishi Paper Industries Co., Ltd.) at a printing speed of 10,000 sheets per hour. .
- H-1, H-2, H-3 and H-4 are known compounds and the structures are as shown below.
- TfO ⁇ represents trifluoromethanesulfonate anion
- TsO ⁇ represents tosylate anion.
- Compounds H-1 to H-4 were synthesized by known methods.
- the lithographic printing plate precursor having the image recording layer containing the specific compound according to the present invention as a polymerization initiator has a heat temporal stability (1), an on-press developability, and a printing durability It turns out that everything is excellent.
- the lithographic printing plate precursor of the comparative example containing a known compound as a polymerization initiator is inferior in any one or more of heat temporal stability (1), the on-press developability and the printing durability.
- Example 201 to 215 and comparative examples 201 to 206 [Preparation of a lithographic printing plate precursor B]
- the support B is used instead of the support A, and the following image recording layer coating solution (2) is used instead of the image recording layer coating solution (1).
- a lithographic printing plate precursor B was produced in the same manner as the above-mentioned lithographic printing plate precursor A except that the following protective layer was formed on the image recording layer.
- the image recording layer coating solution (2) was prepared by mixing and stirring the following photosensitive solution (2) and microgel solution immediately before coating.
- the infrared absorber, the specific compound and the polymerization initiator in the image recording layer coating solution (2) used in the preparation of each lithographic printing plate precursor are summarized in Table 2.
- Acid color-developing agent 2'-anilino-6 '-(N-ethyl-N-isopentylamino) -3'-methylspiro [phthalide-3,9'-xanthene] (S-205, Fukui Yamada Chemical Industry Co., Ltd. )) 0.080g ⁇
- Fluorinated surfactant (1) [above]: 0.008 g
- 2-butanone 1.091 g
- 1-Methoxy-2-propanol 8.609 g
- Microgel solution > ⁇ Microgel (1) [above]: 2.640 g Distilled water: 2.425 g
- the structure of the infrared absorber (D-2) used for the photosensitive solution (2) is shown below.
- the infrared absorber (D-2) is Compound 1 described above.
- a protective layer coating solution having the following composition was bar-coated on the image recording layer, and oven-dried at 120 ° C. for 60 seconds to form a protective layer having a dry coating amount of 0.15 g / m 2 .
- CKS 50 manufactured by Japan Synthetic Chemical Industry Co., Ltd., Sulfonic acid modified, saponification degree 99 mol% or more, polymerization degree 300
- PVA-405 manufactured by Kura
- the preparation method of the inorganic layered compound dispersion liquid (1) is described below.
- ⁇ Preparation of Inorganic Layered Compound Dispersion (1)> To 193.6 g of ion-exchanged water, 6.4 g of synthetic mica (Somasif ME-100, manufactured by Coop Chemical Co., Ltd.) was added, and dispersed using a homogenizer until the average particle size (laser scattering method) became 3 ⁇ m. The aspect ratio of the obtained dispersed particles was 100 or more.
- the exposure was performed under the environment of 25 ° C. and 50% RH.
- the color development of the lithographic printing plate precursor was measured. The measurement was performed by a SCE (regular reflection light removal) method using a spectrophotometer CM2600d manufactured by Konica Minolta Co., Ltd. and operation software CM-S100W.
- the color development was evaluated by the difference ⁇ L between the L * value of the exposed area and the L * value of the unexposed area, using the L * value (brightness) of the L * a * b * color system.
- Table 2 shows the values of ⁇ L. The larger the value of ⁇ L, the better the color developability, and the better the plate inspection properties of the lithographic printing plate by color development.
- ⁇ Temperature stability over time (2) (ring color preventing property)>
- the lithographic printing plate precursor was conditioned at 25 ° C. under a 60% environment for 1 hour and then packaged. The package was then heat aged at 60 ° C. for 4 days. After the completion of heat aging, the points colored in a ring shape were visually counted in an area range of 50 ⁇ 300 mm.
- the ring-shaped anti-coloring properties were evaluated by setting A as the number of coloring points, A as 1 to 10, and C as 10 or more.
- the planographic printing plate precursor is required to have no ring-like coloring (B and C are indicators for expressing the difference in degree of ring-like coloring).
- I-1-j-1, I-7-j-1, I-9-j-1, I-10-j-1, I-12-j described in the column of "specific compound” -1, I-16-j-1, I-9-j-3, I-13-j-3, I-1-j-9, I-7-j-1, I-1-h-1 , I-7-h-1, I-10-h-1 and I-12-h-1 are specific compounds of the present invention, and their structures are as shown above. Also, H-1, H-2, H-3 and H-4 are known compounds, and their structures are as shown above.
- H-5 and H-6 are known compounds, and their structures are as shown below.
- the lithographic printing plate precursor having the image recording layer containing the specific compound or the parameter defining compound according to the present invention has heat aging stability (1), on-press developability, printing durability, color development It is understood that all of the properties and the heat temporal stability (2) are excellent.
- the lithographic printing plate precursor of the comparative example containing a known polymerization initiator is inferior in any one or more of heat aging stability (1), on-press developability, color developability, and heat aging stability (2) There is.
- the support C is used instead of the support A, and an image recording layer coating liquid (3) of the following composition is used in place of the image recording layer coating liquid (1). It was coated and oven-dried at 70 ° C. for 60 seconds to form an image recording layer having a dry coating amount of 0.6 g / m 2 , whereby a lithographic printing plate precursor C was produced.
- the infrared absorber, the specific compound, and the polymerization initiator in the image recording layer coating solution (3) used in the preparation of each lithographic printing plate precursor are summarized in Table 3.
- the infrared absorbers (D-3), (D-4), TPB and the compounds described in trade names used for the image recording layer coating solution (3) are as follows.
- SR-399 Dipentaerythritol pentaacrylate
- Byk 336 Modified dimethylpolysiloxane copolymer (25 mass% xylene / methoxypropyl acetate solution)
- Klucel M hydroxypropyl cellulose (2% by mass aqueous solution)
- ELVACITE 4026 hyperbranched polymethyl methacrylate (10% by weight 2-butanone solution)
- the preparation method of the polymer particle water dispersion liquid (1) used for the said image recording layer coating liquid (3) is shown below.
- ⁇ Preparation of Polymer Particle Water Dispersion (1)> A four-necked flask is provided with a stirrer, a thermometer, a dropping funnel, a nitrogen introducing pipe, a reflux condenser, and nitrogen gas is introduced to perform deoxygenation, polyethylene glycol methyl ether methacrylate (PEGMA, average repeating unit of ethylene glycol) Number: 50) 10 g, 200 g of distilled water and 200 g of n-propanol were added, and the mixture was heated until the internal temperature reached 70 ° C.
- PEGMA polyethylene glycol methyl ether methacrylate
- the particle size distribution of the polymer particles had a maximum at a particle size of 150 nm.
- the particle size distribution is obtained by taking an electron micrograph of the polymer particles, measuring a total of 5,000 particle sizes on the photograph, and on a logarithmic scale between 0 and the maximum value of the obtained particle size measurements. The frequency of occurrence of each particle size was divided into 50 and plotted. With respect to non-spherical particles, the particle diameter value of spherical particles having the same particle area as the particle area in the photograph is taken as the particle diameter.
- I-1-j-1, I-7-j-1, I-9-j-1, I-10-j-1, I-12-j described in the column of "specific compound” -1, I-16-j-1, I-9-j-3, I-13-j-3, I-1-j-9, I-9-j-1, I-1-h-1 , I-7-h-1 and I-10-h-1 are specific compounds of the present invention, and their structures are as shown above. Also, H-1, H-2, H-3 and H-4 are known compounds, and their structures are as shown above.
- the lithographic printing plate precursor having the image recording layer containing the specific compound or the parameter defining compound according to the present invention has heat aging stability (1), on-press developability, printing durability, color development It is understood that all of the properties and the heat temporal stability (2) are excellent.
- the lithographic printing plate precursor of the comparative example containing a known polymerization initiator is inferior in any one or more of heat aging stability (1), on-press developability, color developability, and heat aging stability (2) There is.
- the above-mentioned support D is used instead of the above-mentioned support A, and an image recording layer coating aqueous solution having the following composition after application instead of the above-mentioned image recording layer coating liquid (1)
- a bar coating of (4) was carried out and oven drying was carried out at 50 ° C. for 60 seconds to form an image recording layer with a dry coating amount of 0.93 g / m 2 , thereby preparing a lithographic printing plate precursor D.
- the infrared absorber, the specific compound and the acid generator in the image recording layer coating solution (4) used in the preparation of each lithographic printing plate precursor are summarized in Table 4.
- the compound described in the trade name used for the image recording layer coating aqueous solution (4), the polymer particle water dispersion (2), and the infrared absorbers (D-5) and (D-6) are as follows.
- Glassol E15 polyacrylic acid ERKOL WX 48/20: polyvinyl alcohol / polyvinyl acetate copolymer
- Zonyl FSO 100 surfactant
- polymer particle aqueous dispersion (2) styrene stabilized with anionic wetting agent Acrylonitrile copolymer (molar ratio 50/50, average particle diameter 61 nm, solid content about 20%)
- -1, I-16-j-1, I-9-j-3, I-13-j-3, I-1-j-9, I-9-j-1, I-1-h-1 , I-7-h-1, I-10-h-1 and I-12-h-1 are specific compounds of the present invention, and their structures are as shown above.
- H-1, H-2, H-3 and H-4 are known compounds, and their structures are as shown above.
- the numerical value as the content represents the dry coating amount, and the unit is g / m 2 .
- the lithographic printing plate precursor having the image recording layer containing the specific compound or the parameter defining compound according to the present invention has heat aging stability (1), on-press developability, printing durability, color development It is understood that all of the properties and the heat temporal stability (2) are excellent.
- the lithographic printing plate precursor of the comparative example containing a known acid generator is inferior in any one or more of thermal aging stability (1), on-press developability, color development and thermal aging stability (2) There is.
- Alkaline etching treatment The above aluminum plate is subjected to etching treatment by spraying using an aqueous solution of caustic soda concentration 2.6 mass%, aluminum ion concentration 6.5 mass%, and temperature 70 ° C., and the aluminum plate is 6 g / m 2 It dissolved. After that, it was rinsed with a spray.
- (B) Desmut treatment The aluminum plate was subjected to spray desmutting treatment using a 1% by mass aqueous nitric acid solution (containing 0.5% by mass of aluminum ion) at a temperature of 30 ° C., and then washed by spraying with water.
- the aqueous solution of nitric acid used in the desmutting treatment was the waste solution from the step of electrochemical graining treatment using alternating current in aqueous nitric acid solution.
- Electrochemical surface roughening treatment was continuously performed using an alternating voltage of 60 Hz.
- the electrolytic solution was an aqueous solution of 10.5 g / L of nitric acid (containing 5 g / L of aluminum ion and 0.007% by mass of ammonium ion), and the liquid temperature was 50 ° C.
- the AC power supply waveform is electrochemically roughened with a carbon electrode as a counter electrode, using a trapezoidal rectangular wave AC with a time TP of 0.8 msec and a duty ratio of 1: 1 at which the current value reaches a peak from zero. went. Ferrite was used for the auxiliary anode.
- the current density was 30 A / dm 2 at the peak value of the current, and the amount of electricity was 220 C / dm 2 at the sum of the amounts of electricity when the aluminum plate was an anode.
- the auxiliary anode was shunted 5% of the current flowing from the power supply. After that, it was rinsed with a spray.
- the aluminum plate was etched at 32 ° C. using an aqueous solution of caustic soda concentration 26 mass% and aluminum ion concentration 6.5 mass% at 32 ° C. to dissolve 0.25 g / m 2 of the aluminum plate
- the aluminum hydroxide-based smut component generated when the electrochemical surface roughening treatment was performed was removed, and the edge portion of the formed pit was dissolved to smooth the edge portion. After that, it was rinsed with a spray.
- Desmut treatment was carried out by spraying an aqueous 15% by weight sulfuric acid solution (containing 4.5% by mass of aluminum ion) having a temperature of 30 ° C., followed by washing with water by spraying.
- the aqueous solution of nitric acid used in the desmutting treatment was the waste solution from the step of electrochemical graining treatment using alternating current in aqueous nitric acid solution.
- Electrochemical surface roughening treatment was continuously performed using an alternating voltage of 60 Hz.
- the electrolytic solution was an aqueous solution of 2.5 g / L of hydrochloric acid (containing 5 g / L of aluminum ion) at a temperature of 35 ° C.
- the AC power supply waveform is electrochemically roughened with a carbon electrode as a counter electrode, using a trapezoidal rectangular wave AC with a time TP of 0.8 msec and a duty ratio of 1: 1 at which the current value reaches a peak from zero. went. Ferrite was used for the auxiliary anode.
- the current density was 25 A / dm 2 at the peak value of the current, and the amount of electricity was 50 C / dm 2 at the sum of the amounts of electricity when the aluminum plate was an anode. After that, it was rinsed with a spray.
- a direct current anodic oxide film of 2.5 g / m 2 is formed at a current density of 15 A / dm 2 using a 15 mass% sulfuric acid aqueous solution (containing 0.5 mass% of aluminum ion) as an electrolytic solution on an aluminum plate Washed with water, dried.
- the average pore diameter (surface average pore diameter) in the surface layer of the anodized film was 10 nm.
- the measurement of the pore diameter in the surface layer of the anodized film uses an ultra-high resolution SEM (S-900 manufactured by Hitachi, Ltd.), and uses a deposition process or the like to impart conductivity at a relatively low acceleration voltage of 12 V.
- the surface was observed at a magnification of 150,000 times without application, and 50 pores were randomly extracted to obtain an average value.
- the standard deviation error was less than ⁇ 10%.
- (I) Hydrophilization treatment In order to ensure the hydrophilicity of the non-image area, the aluminum plate is subjected to a silicate treatment at 60 ° C. for 10 seconds using a 2.5% by weight aqueous solution of sodium silicate No. 3 for 10 seconds, and then supported by water. Body E was produced. The adhesion amount of Si was 9.5 mg / m 2 . The center line average roughness (Ra) of the support E was measured using a needle with a diameter of 2 ⁇ m and was 0.27 ⁇ m.
- undercoat layer coating solution (2) having the following composition was applied onto the above support E so that the dry coating amount would be 20 mg / m 2 to form an undercoat layer.
- the numerical value at the lower right of the parentheses of each structural unit in the polymer (P-2) represents a mass ratio
- the numerical value at the lower right of the parentheses of the ethyleneoxy unit represents a repeating number
- ⁇ Formation of image recording layer> After coating a coating solution (5) of the following composition on the undercoat layer with a bar, it was oven dried at 100 ° C. for 60 seconds to form an image recording layer with a dry coating amount of 1.0 g / m 2 .
- the image recording layer coating solution (5) was prepared by mixing and stirring the following photosensitive solution (5) and a microgel solution immediately before coating.
- Binder polymer (2) [the following structure]: 0.240 g Infrared absorber (D-2) [above] 0.024 g -Specific compound listed in Table 5 (polymerization initiator) or 0.245 g of known polymerization initiator Polymerizable compound: Tris (acryloyloxyethyl) isocyanurate, (NK ester A-9300, manufactured by Shin-Nakamura Chemical Co., Ltd.) 0.192 g ⁇ Colorant [below]: 0.030 g ⁇ Fluorinated surfactant (1) [above]: 0.008 g 2-butanone: 1.091 g 1-Methoxy-2-propanol: 8.609 g
- Me represents a methyl group
- the lower right number of the parenthesis of each structural unit of the said binder polymer (2) represents molar ratio
- ⁇ Printing durability> [Image exposure] The lithographic printing plate precursor was exposed to light with an outer surface drum rotation number of 1000 rpm, a laser output of 70%, and a resolution of 2400 dpi, using a Luxel PLATESETTER T-6000III manufactured by Fujifilm Co., Ltd. equipped with an infrared semiconductor laser. The exposed image included a solid image and a 50% dot chart. [Development processing] Development was carried out at 20 ° C. at a transfer speed of 60 cm / min using a Clean Out Unit + C 85 manufactured by Glunz & Jensen for the lithographic printing plate after exposure, to prepare a lithographic printing plate. The developing solution of the following composition was used for development. This developer is a developer capable of performing the removal of the protective layer, the development and the gumming in one solution.
- the developed lithographic printing plate was attached to a plate cylinder of a printing machine LITHRONE 26, manufactured by Komori Corporation.
- Ecoline 2 Fluji Film Co., Ltd. product
- tap water 2/98 (volume ratio) dampening water and Values-G (N) ink ink (DIC Graphics Co., Ltd. product), LITHRONE 26
- the dampening water and the ink were supplied by the standard automatic printing start method, and printing was performed on Tokiwa Art Paper (76.5 kg) (manufactured by Mitsubishi Paper Mills, Ltd.) at a printing speed of 10,000 sheets per hour. Since the image recording layer was gradually worn out as the number of printed sheets increased, the ink density on the printed matter decreased.
- the number of printed sheets was measured until the value measured by a Gretag densitometer for the halftone dot area rate of 50% halftone dots of the FM screen in the printed matter was 5% lower than the measured value of the 100th printed sheet.
- I-1-j-1, I-5-j-1, I-7-j-1, I-12-j-1, I-16-j described in the column of "specific compound” -1 is a specific compound of the present invention, and its structure is as shown above.
- H-1 and H-2 are known compounds, and their structures are as shown above.
- the lithographic printing plate precursor having the image recording layer containing the specific compound according to the present invention is excellent in all of the heat temporal stability (3) and the printing durability.
- a curable composition capable of producing a lithographic printing plate precursor having excellent on-press developability can be provided. Furthermore, according to the present invention, a curable composition having high heat aging stability can be provided. Further, according to the present invention, it is possible to provide a lithographic printing plate precursor capable of producing a lithographic printing plate having high thermal temporal stability, excellent in on-press developability, and excellent printing durability. Furthermore, according to the present invention, there is provided a lithographic printing plate precursor capable of producing a lithographic printing plate having high thermal stability over time, being excellent in plate inspection properties and on-press developability, and having excellent printing durability. be able to.
- a lithographic printing plate precursor capable of producing a lithographic printing plate having high heat aging stability and excellent printing durability. Furthermore, according to the present invention, it is possible to provide a method of preparing a lithographic printing plate using the above-mentioned lithographic printing plate precursor, and a compound used for the image recording layer of the above-mentioned lithographic printing plate precursor.
Abstract
Description
以下、平版印刷版原版を例に説明する。
画像記録層に含有される光重合開始剤としては、ヨードニウム、スルホニウムなどのオニウムと、カウンターアニオンとしての無機又は有機のアニオンからなる塩化合物が用いられる。カウンターアニオンとしての無機又は有機のアニオンとしては、スルホネートアニオン、カルボキシレートアニオン、テトラフルオロボレートアニオン、ヘキサフルオロホスフェートアニオン、p-トルエンスルホネートアニオン、トシレートアニオンなどが知られている。例えば、特許文献1には、特定構造のジアリールヨードニウムカチオンと特定構造のボレートアニオンからなる塩化合物を光重合開始剤として含有する放射線感光性組成物が記載されている。
ところが、通常の現像処理工程を伴わない機上現像型又は無処理(無現像)型の平版印刷版原版では、平版印刷版原版を印刷機に取り付ける段階で平版印刷版原版上の画像を確認することが困難であり、検版を十分行うことができない。そのため、機上現像型又は無処理(無現像)型平版印刷版原版においては、機上現像に悪影響を与えることなく、露光した段階で画像を確認する手段、即ち、露光領域が発色又は消色する、いわゆるプリントアウト画像が形成されることが要求される。
本発明の他の課題は、高い熱経時安定性を有する硬化性組成物を提供することである。
本発明の他の課題は、高い熱経時安定性を有し、機上現像性に優れ、且つ、優れた耐刷性を有する平版印刷版を作製できる平版印刷版原版を提供することである。
本発明の更に他の課題は、高い熱経時安定性を有し、検版性及び機上現像性に優れ、且つ、優れた耐刷性を有する平版印刷版を作製できる平版印刷版原版を提供することである。
本発明の更に他の課題は、高い熱経時安定性を有し、優れた耐刷性を有する平版印刷版を作製できる平版印刷版原版を提供することである。
本発明の更に他の課題は、上記平版印刷版原版を用いる平版印刷版の作製方法を提供することであり、また、上記平版印刷版原版の画像記録層に用いられる化合物を提供することである。
上記有機アニオンが、分子内に芳香環又は複素環を有する有機アニオンである、〔1〕に記載の硬化性組成物。
上記有機アニオンが、(A)環に結合するスルホンアミドアニオン構造又は環に結合するスルホンイミドアニオン構造を有する有機アニオンである、〔1〕に記載の硬化性組成物。
上記有機アニオンが、下記式(V)で表される有機アニオンである〔2〕に記載の硬化性組成物。
上記Cy1で表される環構造は、アルキルアミド基、アルケニルアミド基、アリールアミド基、アルキルウレア基、アリールウレア基、スルホンアミド構造を有する基、及びスルホンイミド構造を有する基からなる群より選択される少なくとも一つの基を有する芳香環で縮環されており、上記Cy2で表される環構造は、アルキルアミド基、アルケニルアミド基、アリールアミド基、アルキルウレア基、アリールウレア基、スルホンアミド構造を有する基、及びスルホンイミド構造を有する基からなる群より選択される少なくとも一つの基を有する芳香環で縮環されている。
上記有機アニオンが、下記式(VI)で表される有機アニオンである〔4〕に記載の硬化性組成物。
R7~R10の少なくとも一つは、アルキルアミド基、アルケニルアミド基、アリールアミド基、アルキルウレア基、アリールウレア基、スルホンアミド構造を有する基、又はスルホンイミド構造を有する基を表し、
R11~R14の少なくとも一つは、アルキルアミド基、アルケニルアミド基、アリールアミド基、アルキルウレア基、アリールウレア基、スルホンアミド構造を有する基、又はスルホンイミド構造を有する基を表す。
(A)環に結合するスルホンアミドアニオン構造又は環に結合するスルホンイミドアニオン構造を有する有機アニオン、及び
(B)カウンターカチオン
を有する塩化合物を含有する、硬化性組成物。
上記有機アニオンが、下記一般式(I)で表される〔6〕に記載の硬化性組成物。
Xはアルキル基、アリール基、ヘテロアリール基、SO2Ra、SORb、CORc、PO3Rd、PO(Re)(Rf)、又はHを表す。Ra、Rb、Rc、Rd、Re、及びRfは、アルキル基、アルコキシ基、アリール基、ヘテロアリール基、及びHよりなる群から選ばれる基を表す。Ra、Rb、Rc、Rd、Re、又はRfはCyと結合し環を形成しても良い。
上記有機アニオンが、下記一般式(II)で表される〔7〕に記載の硬化性組成物。
Raはアルキル基、アルコキシ基、アリール基、ヘテロアリール基、及びHよりなる群から選ばれる基を表す。RaはCyと結合し環を形成しても良い。
上記有機アニオンが、下記一般式(III)または(IV)で表される〔8〕に記載の硬化性組成物。
一般式(IV)中、R11~R14は、各々独立に、水素原子、又は1価の置換基を表す。
上記カウンターカチオンが、ジアリールヨードニウムカチオン、又はトリアリールスルホニウムカチオンである、〔1〕~〔9〕のいずれか1項に記載の硬化性組成物。
上記カウンターカチオンがシアニン系色素におけるカウンターカチオンである、〔1〕~〔9〕のいずれか1項に記載の硬化性組成物。
上記カウンターカチオンが、アルカリ金属イオン、アルカリ土類金属イオン、又は窒素原子上に正電荷が存在する有機カチオンである、〔1〕~〔9〕のいずれか1項に記載の硬化性組成物。
赤外線吸収剤を更に含む、〔1〕~〔10〕、及び〔12〕のいずれか1項に記載の硬化性組成物。
上記赤外線吸収剤が、シアニン系色素である、〔13〕に記載の硬化性組成物。
重合性化合物を更に含む、〔1〕~〔14〕のいずれか1項に記載の硬化性組成物。
酸発色剤を更に含む、〔1〕~〔15〕のいずれか1項に記載の硬化性組成物。
ポリマー粒子を更に含む、〔1〕~〔16〕のいずれか1項に記載の硬化性組成物。
バインダーポリマーを更に含む、〔1〕~〔17〕のいずれか1項に記載の硬化性組成物。
〔1〕~〔18〕のいずれか1項に記載の平版印刷版用硬化性組成物。
〔1〕~〔19〕のいずれか1項に記載の硬化性組成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。
上記画像記録層上に、保護層を有する、〔20〕に記載の平版印刷版原版。
〔20〕又は〔21〕に記載の平版印刷版原版を画像露光する工程と、
印刷機上で印刷インキ及び湿し水よりなる群から選ばれた少なくとも1つにより、上記画像記録層の未露光部分を除去する工程と、を含む平版印刷版の作製方法。
〔20〕又は〔21〕に記載の平版印刷版原版を画像露光する工程と、
pHが2~11の現像液により上記画像記録層の未露光部分を除去する工程と、を含む平版印刷版の作製方法。
有機アニオンが下記一般式(III)又は(IV)で表され、カウンターカチオンがジアリールヨードニウムカチオン、トリアリールスルホニウムカチオンである化合物。
一般式(IV)中、R11~R14は、各々独立に、水素原子、又は1価の置換基を表す。
有機アニオンが下記一般式(III)又は(IV)で表され、カウンターカチオンがシアニン色素におけるカウンターカチオンである化合物。
一般式(IV)中、R11~R14は、各々独立に、水素原子、又は1価の置換基を表す。
また、本発明によれば、高い熱経時安定性を有する硬化性組成物を提供することができる。
また、本発明によれば、高い熱経時安定性を有し、機上現像性に優れ、且つ、優れた耐刷性を有する平版印刷版を作製できる平版印刷版原版を提供することができる。
更に、本発明によれば、高い熱経時安定性を有し、検版性及び機上現像性に優れ、且つ、優れた耐刷性を有する平版印刷版を作製できる平版印刷版原版を提供することができる。
更に、本発明によれば、高い熱経時安定性を有し、優れた耐刷性を有する平版印刷版を作製できる平版印刷版原版を提供することができる。
更に、本発明によれば、上記平版印刷版原版を用いる平版印刷版の作製方法、上記平版印刷版原版の画像記録層に用いられる化合物を提供することができる。
なお、本明細書中、「xx~yy」の記載は、xx及びyyを含む数値範囲を表す。
また、本明細書において、「(メタ)アクリル」はアクリル及びメタクリルの双方、又は、いずれかを表し、「(メタ)アクリレート」はアクリレート及びメタクリレートの双方、又は、いずれかを表す。
また、本発明において、「質量%」と「重量%」とは同義であり、「質量部」と「重量部」とは同義である。
また、本発明において、2以上の好ましい態様の組み合わせは、より好ましい態様である。
また、本発明における重量平均分子量(Mw)は、特に断りのない限り、TSKgel GMHxL、TSKgel G4000HxL、TSKgel G2000HxL(何れも東ソー(株)製の商品名)のカラムを使用したゲルパーミエーションクロマトグラフィ(GPC)分析装置により、溶媒THF(テトラヒドロフラン)、示差屈折計により検出し、標準物質としてポリスチレンを用いて換算した分子量である。
本明細書において、式で表される化合物における基の表記に関して、置換あるいは無置換を記していない場合、上記基が更に置換基を有することが可能な場合には、他に特に規定がない限り、無置換の基のみならず置換基を有する基も包含する。例えば、式において、「Rはアルキル基、アリール基又は一価のヘテロ環基を表す」との記載があれば、「Rは無置換アルキル基、置換アルキル基、無置換アリール基、置換アリール基、無置換の一価のヘテロ環基又は置換基を有する一価のヘテロ環基を表す」ことを意味する。
本明細書において「工程」との語は、独立した工程だけでなく、他の工程と明確に区別できない場合であっても工程の所期の目的が達成されれば、本用語に含まれる。
第一の態様として、本発明の硬化性組成物は、a)ハンセンのSP値パラメータにおけるδdが16以上、δpが16以上32以下、δHがδpの60%以下である有機アニオン(以下、「a)有機アニオン」又は「第一の有機アニオン」ともいう)、及び、b)カウンターカチオンを有する塩化合物(以下、「パラメータ規定化合物」とも言う)を含有する。
なお、δd、δp、及びδHの単位は、MPa0.5である。
その理由は明らかではないが、以下の通りと推測される。
先ず、本発明らは、インキと湿し水とを用いる平版印刷版原版の機上現像においては、一般に、インキの溶解パラメータ(SP値)と水の溶解パラメータ(SP値)との差が大きいため、機上現像において除去されるべき画像形成層の非画像部は、そもそも、インクと湿し水のそれぞれに対しては親和しにくい環境に曝されており、これが機上現像性の低下の要因になっているものと推測した。
ところで、溶解パラメータ(SP値)としては、ハンセンの溶解パラメータが挙げられ、このハンセンの溶解パラメータとしては、分散性に寄与するδd、極性に寄与するδp、及び、水素結合に寄与するδHが知られているが、今般、本発明者らは、これらの3つのパラメータを用いて規定した有機アニオンを有する特定の塩化合物を硬化性組成物に含有させることによって、平版印刷版原版の機上現像液を向上させることを見出し、上記構成を完成させたものである。
具体的には、先ず、上記塩化合物の有機アニオンにおけるδdを16以上とすることで、この塩化合物間同士には、互いの化合物が有する親油性基と親油性基との相互作用等により、充分な分子間力が発現するように構成されているものと考えられる。これにより、機上現像前においては、画像形成層を所望の状態としつつ、機上現像時においては、インキが上記相互作用を緩和するなどして、上記分子間力を低減しやすくなっているものと考えられる。
また、上記塩化合物の有機アニオンにおけるδpを16以上とすることで、この塩化合物の極性度を高めることにより、機上現像時においては、画像形成層の非画像部が、水に対しても親和するものと考えられる。
しかしながら、本発明者らは、鋭意検討の結果、単に、δpが16以上の有機アニオンを有する塩化合物を画像記録層が含有させればよいのではなく、先ず、δpを32以下とする必要があることを見出した。これは、塩化合物の極性度が高すぎると、インキに対する非親和度が大きくなり、その結果、非画像部の除去がスムーズに進まないことによるものと推測される。
また、本発明者らは、鋭意検討の結果、δHがδpの60%以下とする必要もあることを見出した。これは、詳細な理由は不明ではあるが、インキと湿し水とを用いる平版印刷版原版の機上現像においては、δpに対してδHを一定値以下とした上で、すなわち、水素結合による寄与を一定以下とした上で、上記塩化合物の極性度を高めることが、非画像部の除去、ひいては、機上現像性の向上に必要になるものと推察している。
以上のように、上記塩化合物は、平版印刷版原版の機上現像時に存在するインキ及び湿し水に対して選択的に溶媒和する性質を有し、ひいては、インキ及び湿し水の両方に対して親和性を有するものと考えられる。その結果、本発明の第一の態様に係る硬化性組成物は、機上現像性に優れる平版印刷版原版を作製できるものと考えられる。
ハンセンのSP値パラメータにおけるδdの上限値は特に限定されないが、好ましくは32以下であり、更に好ましくは28以下である。
δHはδpの20%以上が好ましく、δpの30%以上が更に好ましい。
上記a)有機アニオンは、上記「ハンセンのSP値パラメータにおけるδdが16以上、δpが16以上32以下、δHがδpの60%以下である」を満たしやすいという観点から、分子内に芳香環又は複素環を有する有機アニオンであることが好ましい。
芳香環は、具体的には芳香族炭化水素環であり、芳香族炭化水素環としては、炭素数6~20の芳香族炭化水素環が挙げられ、具体的には、ベンゼン、ナフタレン、アントラキノンなどが挙げられる。
複素環は、酸素原子、硫黄原子及び窒素原子から選ばれる少なくとも1つの複素原子を含む複素環である。複素環は5員環~8員環が好ましい。複素環は飽和でも不飽和でもよい。複素環は、芳香族の複素環が好ましい。
複素環の例としては、ピリジン環、ピリミジン環、ピロリン環などが挙げられる。
上記Cy1で表される環構造は、アルキルアミド基、アルケニルアミド基、アリールアミド基、アルキルウレア基、アリールウレア基、スルホンアミド構造を有する基、及びスルホンイミド構造を有する基からなる群より選択される少なくとも一つの基を有する芳香環で縮環されており、上記Cy2で表される環構造は、アルキルアミド基、アルケニルアミド基、アリールアミド基、アルキルウレア基、アリールウレア基、スルホンアミド構造を有する基、及びスルホンイミド構造を有する基からなる群より選択される少なくとも一つの基を有する芳香環で縮環されている。
上記芳香環としては、例えば、ベンゼン環、ナフタレン環、アントラセン環どが挙げられる。
芳香環は、置換基を有していてもよく、置換基の例としては、アルキル基などが挙げられる。
R7~R10の少なくとも一つは、アルキルアミド基、アルケニルアミド基、アリールアミド基、アルキルウレア基、アリールウレア基、スルホンアミド構造を有する基、又はスルホンイミド構造を有する基を表し、
R11~R14の少なくとも一つは、アルキルアミド基、アルケニルアミド基、アリールアミド基、アルキルウレア基、アリールウレア基、スルホンアミド構造を有する基、又はスルホンイミド構造を有する基を表す。
アルキルアミド基、アルケニルアミド基、アリールアミド基、アルキルウレア基、アリールウレア基、スルホンアミド構造を有する基、又はスルホンイミド構造を有する基は、それぞれ、上記Cy1、又はCy2で表される環構造が縮環される芳香環が有する、アルキルアミド基、アルケニルアミド基、アリールアミド基、アルキルウレア基、アリールウレア基、スルホンアミド構造を有する基、及びスルホンイミド構造を有する基からなる群より選択される少なくとも一つの基における、アルキルアミド基、アルケニルアミド基、アリールアミド基、アルキルウレア基、アリールウレア基、スルホンアミド構造を有する基、及びスルホンイミド構造を有する基と同様であり、好ましい範囲も同様である。
b)カウンターカチオンは、後述の(B)カウンターカチオンと同様である。
第二の態様として、本発明の硬化性組成物は(A)環に結合するスルホンアミドアニオン構造又は環に結合するスルホンイミドアニオン構造を有する有機アニオン(以下、「(A)有機アニオン」又は「第二の有機アニオン」ともいう)、及び、(B)カウンターカチオンを有する塩化合物を含有する。
(A)有機アニオンにおけるスルホンアミドアニオン構造とは、下記のスルホンアミド構造から水素原子が除去されたアニオン構造を表す。なお、下記構造において、*は結合手を表す。
脂環炭化水素環としては、炭素数3~30の脂環炭化水素環が挙げられる。なお、脂環炭化水素環は、不飽和結合を有しても良い。
複素環は、酸素原子、硫黄原子及び窒素原子から選ばれる少なくとも1つの複素原子を含む複素環である。複素環は5員環~8員環が好ましい。複素環は飽和でも不飽和でもよい。複素環は、芳香族の複素環が好ましい。
複素環の例としては、ピリジン環、ピリミジン環、ピロリン環などが挙げられる。
Xはアルキル基、アリール基、ヘテロアリール基、SO2Ra、SORb、CORc、PO3Rd、PO(Re)(Rf)、又はHを表す。Ra、Rb、Rc、Rd、Re、及びRfは、アルキル基、アルコキシ基、アリール基、ヘテロアリール基、及びHよりなる群から選ばれる基を表す。Ra、Rb、Rc、Rd、Re、又はRfは、Cyと結合し環を形成しても良い。
不飽和結合を有しても良い脂環基の例としては、シクロペンタニル基、シクロペンタジエニル基、シクロヘキセニル基、シクロヘキサジエニル基、シクロヘプタニル基、シクロヘプタジエニル基、ノルボルネン基などが挙げられる。
また、Ra、Rb、Rc、Rd、Re、Rf及びRgで表される、アルキル基、アルコキシ基、アリール基、又は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、アルキル基、アルコキシ基、アリールオキシ基、アリール基、カルボニル基、アルコキシカルボニル基、シアノ基、アミド基、ウレア基、ウレタン基、アルケニル基、アリル基、アクリル基、メタクリル基、アクリルアミド基、メタクリルアミド基、ハロゲン原子の1種又は2種以上が組み合わされてなる基などが挙げられる。
Ra、Rb、Rc、Rd、Re、又はRfは、Cyと結合し環を形成しても良い。なお、XがSO2Raであり、RaがH(水素原子)であり、Raが、Cyと結合し環を形成するとは、RaとしてのHが脱離して、SO2がCyと結合することを表すものである。
Raはアルキル基、アルコキシ基、アリール基、ヘテロアリール基、及びHよりなる群から選ばれる基を表す。RaはCyと結合し環を形成しても良い。
一般式(II)におけるRaは、一般式(I)のXにおけるRaと同様であり、好ましい範囲も同様である。
また、Raで表されるアルキル基、アルコキシ基、アリール基、又は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、アルキル基、アルコキシ基、アリールオキシ基、アリール基、カルボニル基、アルコキシカルボニル基、シアノ基、アミド基、ウレア基、ウレタン基、アルケニル基、アリル基、アクリル基、メタクリル基、アクリルアミド基、メタクリルアミド基、ハロゲン原子の1種又は2種以上が組み合わされてなる基などが挙げられる。
一般式(IV)中、R11~R14は、各々独立に、水素原子、又は1価の置換基を表す。
1価の置換基として挙げた基は、他の基で更に置換されていても良い。
1価の置換基として挙げた基は、他の基で更に置換されていても良い。
X1は、SO2Ra、SORb、CORc、PO3Rd、又はPO(Re)(Rf)を表す。Ra、Rb、Rc、Rd、Re、及びRfは、アルキル基、アルコキシ基、アリール基、ヘテロアリール基、及びHよりなる群から選ばれる基を表す。Ra、Rb、Rc、Rd、Re、又はRfは、Cy1と結合し環を形成しても良い。
Cy1におけるアリール基、ヘテロアリール基は、Cyにおけるアリール基、ヘテロアリール基と同様であり、好ましい範囲も同様である。
一般式(IA)におけるRa、Rb、Rc、Rd、Re、及びRfとしてのアルキル基、アルコキシ基、アリール基、ヘテロアリール基は、一般式(I)におけるRa、Rb、Rc、Rd、Re、及びRfとしてのアルキル基、アルコキシ基、アリール基、ヘテロアリール基と同様であり、好ましい範囲も同様である。
本発明に係る特定化合物を構成するカウンターカチオン((B)カウンターカチオン)は、上記アルミニウム原子又はリン原子上に負電荷が存在する有機アニオンとイオン結合により塩化合物を形成しうるカチオンであればよい。
カウンターカチオンは、無機カチオンであっても有機カチオンであってもよい。無機カチオンとしては、リチウムイオン、ナトリウムイオン、カリウムイオンなどのアルカリ金属イオン、カルシウム、マグネシウムイオン、カルシウムイオンなどのアルカリ土類金属イオンなどが挙げられる。
有機カチオンとしては、窒素原子上に正電荷が存在する有機カチオンが挙げられる。窒素原子上に正電荷が存在する有機カチオンは、式:N+(R01)(R02)(R03)(R04)(ここで、R01、R02、R03、R04は、それぞれ独立に、アルキル基又はアリール基を表す)で表されるアンモニウムカチオン、ピリジニウムカチオン、イミダゾリウムカチオンなどを包含する。
アンモニウムカチオンの例としては、テトラメチルアンモニウム、テトラエチルアンモニウム、テトラブチルアンモニウムなどが挙げられる。
具体的なアニオン部およびカチオン部の構造の例は上記の通りであるが、本発明はこれらに限定されるものではない。
また、実施例においては、特定化合物はI-1-j-1のように、アニオン部とカチオン部を記載した形で表される。
また、特定化合物を含有する本発明の第二の組成物は、赤外線露光に起因する赤外線吸収剤から特定化合物への電子移動効率あるいは光熱変換効率に優れる。このため、重合性化合物の重合あるいは熱融着といった硬化反応が促進され、良好な硬化性を示すと考えられる。従って、例えば、本発明の組成物を適用した平版印刷版原版から作製された平版印刷版は、優れた耐刷性を有する。
更に、特定化合物を構成する有機アニオンは、スルホンアミドアニオン構造又はスルホンイミドアニオン構造が窒素原子上に負電荷を有しており、比較的親水性な部分と、その周辺に存在するで、疎水部として剛直な環構造を有する比較的疎水性部分を有するため、乳化性を有すると考えられる。このため、例えば、本発明の組成物を適用した平版印刷版原版は、良好な機上現像性を示す。
更に、特定化合物を構成する有機アニオンは、酸として機能するので、後述するように、本発明の組成物にロイコ染料などの酸発色剤を併用することにより、発色画像を形成することができる。特定化合物を構成する有機アニオンは発色性能に優れており、従って、例えば、本発明の組成物を適用した平版印刷版原版は、優れた検版性を示す。
更に、無機アニオンとして公知のPF6 -を含む重合開始剤をロイコ染料などの酸発色剤と併用した平版印刷版原版は、熱経時でリング状発色を生じるという問題がある。リング状発色は、平版印刷版原版の全表面にわたって、微細なリング状の発色が生じる現象で、検版作業の妨げとなる。PF6 -の代わりに、本発明に係る有機アニオンを含む重合開始剤をロイコ染料などの酸発色剤と併用した平版印刷版原版は、熱経時でリング状発色を生じないという利点がある。
<1>
有機アニオンが下記一般式(III)又は(IV)で表され、カウンターカチオンがジアリールヨードニウムカチオン、トリアリールスルホニウムカチオンである化合物。
一般式(IV)中、R11~R14は、各々独立に、水素原子、又は1価の置換基を表す。
<2>
有機アニオンが下記一般式(III)又は(IV)で表され、カウンターカチオンがシアニン色素におけるカウンターカチオンである化合物。
一般式(IV)中、R11~R14は、各々独立に、水素原子、又は1価の置換基を表す。
ジアリールヨードニウムカチオン、トリアリールスルホニウムカチオンは、前述したジアリールヨードニウムカチオン、トリアリールスルホニウムカチオンと同義であり、好ましい範囲も同義である。
形態(1)の組成物は、特定化合物、赤外線吸収剤、バインダーポリマー及びポリマー粒子の1つ以上、及び重合性化合物を含む。
形態(2)の組成物は、特定化合物、酸発色剤、赤外線吸収剤、バインダーポリマー及びポリマー粒子の1つ以上、及び重合性化合物を含む。
形態(3)の組成物は、特定化合物、酸発色剤、赤外線吸収剤、バインダーポリマー及びポリマー粒子の1つ以上、重合性化合物、及び重合開始剤を含む。
形態(1)の組成物における特定化合物は、カウンターカチオンが、ジアリールヨードニウムカチオンまたはトリアリールスルホニウムカチオンである重合開始剤であることが好ましい。
形態(2)の組成物における特定化合物は、カウンターカチオンが、ジアリールヨードニウムカチオンまたはトリアリールスルホニウムカチオンである重合開始剤であることが好ましい。
形態(3)の組成物における特定化合物は、カウンターカチオンが、アルカリ金属イオン、アルカリ土類金属イオン又は窒素原子上に電荷をもつ有機カチオンである添加剤であることが好ましい。
本発明の組成物は、赤外線吸収剤を含有することが好ましい。赤外線吸収剤は、赤外線により励起して重合開始剤等に電子移動及び/又はエネルギー移動する機能を有する。また、吸収した赤外線を熱に変換する機能を有する。赤外線吸収剤は、750~1,400nmの波長域に極大吸収を有することが好ましい。赤外線吸収剤としては、染料又は顔料が挙げられ、染料が好ましく用いられる。
染料のうち、シアニン色素、スクアリリウム色素、ピリリウム塩が好ましく、シアニン色素がより好ましく、インドレニンシアニン色素が特に好ましい。
また、特開平5-5005号公報の段落0008~0009、特開2001-222101号公報の段落0022~0025に記載の化合物も好ましく使用することができる。
顔料としては、特開2008-195018号公報の段落0072~0076に記載の化合物が好ましい。
赤外線吸収剤は、組成物中に任意の量含有させることができる。の赤外線吸収剤の含有量は、組成物の全固形分中、0.05~30質量%が好ましく、0.1~20質量%がより好ましく、0.2~10質量%が更に好ましい。
本発明の組成物は、重合性化合物を含有することが好ましい。重合性化合物は、例えば、ラジカル重合性化合物であっても、カチオン重合性化合物であってもよいが、少なくとも1個のエチレン性不飽和結合を有する付加重合性化合物(エチレン性不飽和化合物)であることが好ましい。エチレン性不飽和化合物としては、末端エチレン性不飽和結合を少なくとも1個有する化合物が好ましく、末端エチレン性不飽和結合を2個以上有する化合物がより好ましい。重合性化合物は、例えばモノマー、プレポリマー、即ち、2量体、3量体若しくはオリゴマー、又は、それらの混合物などの化学的形態を持つことができる。
CH2=C(RM4)COOCH2CH(RM5)OH (M)
式(M)中、RM4及びRM5はそれぞれ独立に、水素原子又はメチル基を表す。
重合性化合物の含有量は、組成物の全固形分中、5~75質量%が好ましく、10~70質量%がより好ましく、15~60質量%が更に好ましい。
本発明の組成物は、重合開始剤を含有することが好ましい。重合開始剤は、光、熱あるいはその両方のエネルギーによりラジカルやカチオン等の重合開始種を発生する化合物であり、公知の熱重合開始剤、結合解離エネルギーの小さな結合を有する化合物、光重合開始剤などから適宜選択して用いることができる。
重合開始剤としては、赤外線感光性重合開始剤が好ましい。また、重合開始剤としては、ラジカル重合開始剤が好ましい。
ラジカル重合開始剤としては、例えば、有機ハロゲン化物、カルボニル化合物、アゾ化合物、有機過酸化物、メタロセン化合物、アジド化合物、ヘキサアリールビイミダゾール化合物、ジスルホン化合物、オキシムエステル化合物、及び、オニウム塩化合物が挙げられる。
カルボニル化合物としては、例えば、特開2008-195018号公報の段落0024に記載の化合物が好ましい。
アゾ化合物としては、例えば、特開平8-108621号公報に記載のアゾ化合物等が挙げられる。
有機過酸化物としては、例えば、特開2008-195018号公報の段落0025に記載の化合物が好ましい。
メタロセン化合物としては、例えば、特開2008-195018号公報の段落0026に記載の化合物が好ましい。
アジド化合物としては、例えば、2,6-ビス(4-アジドベンジリデン)-4-メチルシクロヘキサノン等の化合物が挙げられる。
ヘキサアリールビイミダゾール化合物としては、例えば、特開2008-195018号公報の段落0027に記載の化合物が好ましい。
ジスルホン化合物としては、例えば、特開昭61-166544号、特開2002-328465号の各公報に記載の化合物が挙げられる。
オキシムエステル化合物としては、例えば、特開2008-195018号公報の段落0028~0030に記載の化合物が好ましい。
重合開始剤の含有量は、組成物の全固形分中、0.1~50質量%が好ましく、0.5~30質量%がより好ましく、0.8~20質量%が更に好ましい。
本発明の組成物は、バインダーポリマーを含有することが好ましい。バインダーポリマーとしては、皮膜性を有するポリマーが好ましく、組成物に用いられる公知のバインダーポリマーを好適に使用することができる。中でも、バインダーポリマーとしては、(メタ)アクリル樹脂、ポリビニルアセタール樹脂、ポリウレタン樹脂が好ましい。
機上現像用バインダーポリマーとしては、アルキレンオキサイド鎖を有するバインダーポリマーが好ましい。アルキレンオキサイド鎖を有するバインダーポリマーは、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い。また、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)含有繰返し単位で構成されるブロックと(アルキレンオキサイド)非含有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。
ポリ(アルキレンオキサイド)部位を主鎖に有する場合は、ポリウレタン樹脂が好ましい。ポリ(アルキレンオキサイド)部位を側鎖に有する場合の主鎖のポリマーとしては、(メタ)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、ポリスチレン樹脂、ノボラック型フェノール樹脂、ポリエステル樹脂、合成ゴム、天然ゴムが挙げられ、特に(メタ)アクリル樹脂が好ましい。
ポリ(アルキレンオキサイド)部位におけるアルキレンオキサイドの繰返し数は2~120が好ましく、2~70がより好ましく、2~50が更に好ましい。
アルキレンオキサイドの繰返し数が120以下であれば、摩耗による耐刷性、インキ受容性による耐刷性の両方が低下することがなく好ましい。
一価の有機基としては、炭素数1~6のアルキル基が好ましい。具体的には、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、sec-ブチル基、イソブチル基、tert-ブチル基、n-ペンチル基、イソペンチル基、ネオペンチル基、n-ヘキシル基、イソヘキシル基、1,1-ジメチルブチル基、2,2-ジメチルブチル基、シクロペンチル基及びシクロヘキシル基が挙げられる。
式(AO)において、yは2~70が好ましく、2~50がより好ましい。R1は水素原子又はメチル基が好ましく、水素原子が特に好ましい。R2は水素原子又はメチル基が特に好ましい。
分子の主鎖中にエチレン性不飽和結合を有する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、-CH2CH=CH2、-CH2CH2-Y(式中、Yはシクロヘキセン残基を表す。)及び-CH2CH2-OCO-CH=CH2が挙げられる。
また、本発明において、オリゴマーは、Mw800以上2,000未満のものとし、ポリマーは、Mw2,000以上のものとする。
本発明において、体積平均一次粒径は、粒子の電子顕微鏡写真を撮影し、写真上で粒子の粒径を総計で5000個測定し、算術平均値を算出することにより得られる。
非球形粒子については写真上の粒子面積と同一の粒子面積を持つ球形粒子の粒径値を粒径(円相当径)として測定する。
上記体積平均一次粒径の測定方法は、特別な記載がない限り、粒子の形状で存在するバインダーポリマー以外の粒子についても同様である。
バインダーポリマーは、組成物中に任意の量で含有させることができる。バインダーポリマーの含有量は、本発明の組成物の用途などにより適宜選択できるが、組成物の全固形分中、1~90質量%が好ましく、5~80質量%がより好ましい。
本発明の組成物は酸発色剤を含有することができる。酸発色剤は、電子受容性化合物(例えば酸等のプロトン)を受容することにより、発色する性質を有する化合物である。酸発色剤としては、ラクトン、ラクタム、サルトン、スピロピラン、エステル、アミド等の部分骨格を有し、電子受容性化合物と接触した時に、速やかにこれらの部分骨格が開環若しくは開裂する無色の化合物が好ましい。
発色後の色素の色相としては、可視性の観点から、緑、青又は黒であることが好ましい。
酸発色剤の含有量は、本発明の組成物の全固形分中、0.1~20質量%が好ましく、1~15質量%がより好ましく、2~10質量%が更に好ましい。
酸発生剤の含有量は、本発明の組成物の全固形分中、1~30質量%が好ましく、3~20質量%がより好ましく、6~15質量%が更に好ましい。
本発明の組成物は、ラジカル生成助剤を含有してもよい。ラジカル生成助剤は、本発明の組成物を平版印刷版原版の画像記録層に適用する場合、平版印刷版原版から作製される平版印刷版の耐刷性向上に寄与する。ラジカル生成助剤としては、例えば、以下の5種類が挙げられる。(i)アルキル又はアリールアート錯体:酸化的に炭素-ヘテロ結合が解裂し、活性ラジカルを生成すると考えられる。具体的には、ボレート化合物等が挙げられる。(ii)アミノ酢酸化合物:酸化により窒素に隣接した炭素上のC-X結合が解裂し、活性ラジカルを生成するものと考えられる。Xとしては、水素原子、カルボキシ基、トリメチルシリル基又はベンジル基が好ましい。具体的には、N-フェニルグリシン類(フェニル基に置換基を有していてもよい。)、N-フェニルイミノジ酢酸(フェニル基に置換基を有していてもよい。)等が挙げられる。(iii)含硫黄化合物:上述のアミノ酢酸化合物の窒素原子を硫黄原子に置き換えたものが、同様の作用により活性ラジカルを生成し得る。具体的には、フェニルチオ酢酸(フェニル基に置換基を有していてもよい。)等が挙げられる。(iv)含錫化合物:上述のアミノ酢酸化合物の窒素原子を錫原子に置き換えたものが、同様の作用により活性ラジカルを生成し得る。(v)スルフィン酸塩類:酸化により活性ラジカルを生成し得る。具体的は、アリールスルフィン駿ナトリウム等が挙げられる。
ボレート化合物が有する対カチオンとしては、アルカリ金属イオン又はテトラアルキルアンモニウムイオンが好ましく、ナトリウムイオン、カリウムイオン又はテトラブチルアンモニウムイオンがより好ましい。
ラジカル生成助剤の含有量は、本発明の組成物の全固形分中、0.01~30質量%が好ましく、0.05~25質量%がより好ましく、0.1~20質量%が更に好ましい。
本発明の組成物が平版印刷版原版の画像記録層に適用される場合、平版印刷版原版の機上現像性向上の観点から、本発明の組成物は、ポリマー粒子を含有してもよい。ポリマー粒子は、熱、好ましくは露光により発生する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ポリマー粒子であることが好ましい。
ポリマー粒子は、熱融着性粒子、熱反応性ポリマー粒子、重合性基を有するポリマー粒子、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(架橋ポリマー粒子)から選ばれる少なくとも1つであることが好ましい。中でも、重合性基を有するポリマー粒子及びミクロゲルが好ましい。
熱融着性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もしくはコポリマー又はそれらの混合物が挙げられる。好ましくは、ポリスチレン、スチレン及びアクリロニトリルを含む共重合体、ポリメタクリル酸メチルが挙げられる。熱融着性粒子の数平均一次粒径は0.01~2.0μmが好ましい。
マイクロカプセルやミクロゲルの体積平均粒径は、0.01~3.0μmが好ましく、0.05~2.0μmがより好ましく、0.10~1.0μmが更に好ましい。この範囲内で良好な解像度と経時安定性が得られる。
体積平均粒径は、動的光散乱式粒径分布測定装置 LB-500((株)堀場製作所製)を用いて、光散乱法によりにより測定される。
ポリマー粒子の含有量は、本発明の組成物の全固形分中、5~90質量%が好ましい。
本発明の組成物は、連鎖移動剤を含有してもよい。連鎖移動剤は、本発明の組成物が平版印刷版原版の画像記録層に適用される場合、平版印刷版原版から作製される平版印刷版における耐刷性の向上に寄与する。
連鎖移動剤としては、チオール化合物が好ましく、沸点(揮発し難さ)の観点で炭素数7以上のチオールがより好ましく、芳香環上にメルカプト基を有する化合物(芳香族チオール化合物)が更に好ましい。チオール化合物は単官能チオール化合物であることが好ましい。
連鎖移動剤の含有量は、本発明の組成物の全固形分中、0.01~50質量%が好ましく、0.05~40質量%がより好ましく、0.1~30質量%が更に好ましい。
本発明の組成物は、平版印刷版原版の画像記録層に適用される場合、平版印刷版原版から作製される平版印刷版の耐刷性を低下させることなく、平版印刷版原版の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は、分子量1,000未満の化合物が好ましく、分子量800未満の化合物がより好ましく、分子量500未満の化合物が更に好ましい。
低分子親水性化合物としては、例えば、水溶性有機化合物としては、エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、ジプロピレングリコール、トリプロピレングリコール等のグリコール類及びそのエーテル又はエステル誘導体類、グリセリン、ペンタエリスリトール、トリス(2-ヒドロキシエチル)イソシアヌレート等のポリオール類、トリエタノールアミン、ジエタノールアミン、モノエタノールアミン等の有機アミン類及びその塩、アルキルスルホン酸、トルエンスルホン酸、ベンゼンスルホン酸等の有機スルホン酸類及びその塩、アルキルスルファミン酸等の有機スルファミン酸類及びその塩、アルキル硫酸、アルキルエーテル硫酸等の有機硫酸類及びその塩、フェニルホスホン酸等の有機ホスホン酸類及びその塩、酒石酸、シュウ酸、クエン酸、リンゴ酸、乳酸、グルコン酸、アミノ酸類等の有機カルボン酸類及びその塩、ベタイン類等が挙げられる。
低分子親水性化合物の含有量は、本発明の組成物の全固形分中、0.5~20質量%が好ましく、1~15質量%がより好ましく、2~10質量%が更に好ましい。
本発明の組成物は、平版印刷版原版の画像記録層に適用される場合、平版印刷版原版から作製される平版印刷版におけるインキの着肉性(以下、単に「着肉性」ともいう)を向上させるために、ホスホニウム化合物、含窒素低分子化合物、アンモニウム基含有ポリマー等の感脂化剤を含有してもよい。特に、平版印刷版原版が保護層に無機層状化合物を含有する場合、これらの化合物は、無機層状化合物の表面被覆剤として機能し、無機層状化合物による印刷途中の着肉性低下を抑制することができる。
感脂化剤としては、ホスホニウム化合物と、含窒素低分子化合物と、アンモニウム基含有ポリマーとを併用することが好ましく、ホスホニウム化合物と、第四級アンモニウム塩類と、アンモニウム基含有ポリマーとを併用することがより好ましい。
本発明の平版印刷版原版の画像記録層は、可視光域に大きな吸収を持つ染料を画像の着色剤として含有することができる。具体的には、オイルイエロー#101、オイルイエロー#103、オイルピンク#312、オイルグリーンBG、オイルブルーBOS、オイルブルー#603、オイルブラックBY、オイルブラックBS、オイルブラックT-505(以上オリエント化学工業(株)製)、ビクトリアピュアブルー、クリスタルバイオレット(CI42555)、メチルバイオレット(CI42535)、エチルバイオレット、エチルバイオレット6HNAPS、ローダミンB(CI145170B)、マラカイトグリーン(CI42000)、メチレンブルー(CI52015)及び特開昭62-293247号に記載されている染料を挙げることができる。また、フタロシアニン系顔料、アゾ系顔料、カーボンブラック、酸化チタン等の顔料も好適に用いることができる。着色剤を含有させることにより、画像形成後の画像部と非画像部の区別がつきやすくなるので、含有させることが好ましい。
着色剤の添加量は、画像記録層の全固形分に対して、0.005~10質量%が好ましい。
本発明の組成物は、その他の成分として、界面活性剤、重合禁止剤、高級脂肪酸誘導体、可塑剤、無機粒子、無機層状化合物等を含有することができる。具体的には、特開2008-284817号公報の段落0114~0159に記載された各成分を含有することができる。
本発明の平版印刷版原版は、本発明の組成物を含有する画像記録層を支持体上に有する。
以下に、本発明の組成物の特徴が顕著に発現される機上現像型の平版印刷版原版を例として説明するが、現像処理により平版印刷版を作製する現像処理型の平版印刷版原版についても適宜説明する。
画像記録層の1つの形態によれば、画像記録層は、赤外線吸収剤、重合性化合物、重合開始剤、並びに、バインダーポリマー及びポリマー粒子の少なくとも1つを含有する。画像記録層は、更に、ラジカル生成助剤、及び、連鎖移動剤を含有することが好ましい。
画像記録層のもう1つの形態によれば、画像記録層は、赤外線吸収剤、熱融着性粒子、及び、バインダーポリマーを含有する。
平版印刷版原版の検版性を向上させるため、画像記録層には、酸発色剤を含有させることができる。
上記画像記録層において、重合開始剤、赤外線吸収剤として、本発明に係る特定化合物を用いることができる。また、酸発色剤を含有する画像記録層においては、酸発色剤に対する酸発生剤として、本発明に係る特定化合物を用いることができる。
画像記録層に含有される赤外線吸収剤、重合性化合物、重合開始剤、バインダーポリマー、ポリマー粒子、ラジカル生成助剤、連鎖移動剤、熱融着性粒子などの各成分、並びに、その含有量については、上記本発明の組成物における記載を参照することができる。
画像記録層は、例えば、特開2008-195018号公報の段落0142~0143に記載のように、必要な上記各成分を溶剤に分散又は溶解して塗布液を調製し、塗布液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、乾燥することにより形成することができる。
溶剤としては、公知の溶剤を用いることができる。具体的には、例えば、水、アセトン、メチルエチルケトン(2-ブタノン)、シクロヘキサン、酢酸エチル、エチレンジクロライド、テトラヒドロフラン、トルエン、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールジメチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、アセチルアセトン、シクロヘキサノン、ジアセトンアルコール、エチレングリコールモノメーチルエーテルアセテート、エチレングリコールエチルエーテルアセテート、エチレングリコールモノイソプロピルエーテル、エチレングリコールモノブチルエーテルアセテート、1-メトキシ-2-プロパノール、3-メトキシ-1-プロパノール、メトキシメトキシエタノール、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、3-メトキシプロピルアセテート、N,N-ジメチルホルムアミド、ジメチルスルホキシド、γ-ブチロラクトン、乳酸メチル、乳酸エチル等が挙げられる。溶剤は、1種単独で使用してもよいし、2種以上を併用してもよい。塗布液中の固形分濃度は1~50質量%程度であることが好ましい。
塗布、乾燥後における画像記録層の塗布量(固形分)は、用途によって異なるが、良好な感度と画像記録層の良好な皮膜特性を得る観点から、0.3~3.0g/m2程度が好ましい。
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)を有することが好ましい。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、耐刷性を損なわずに現像性を向上させることに寄与する。また、赤外線レーザー露光の場合に、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することによる感度の低下を防ぐ効果も有する。
支持体表面に吸着可能な吸着性基としては、フェノール性ヒドロキシ基、カルボキシ基、-PO3H2、-OPO3H2、-CONHSO2-、-SO2NHSO2-、-COCH2COCH3が好ましい。親水性基としては、スルホ基又はその塩、カルボキシ基の塩が好ましい。架橋性基としては、アクリル基、メタクリル基、アクリルアミド基、メタクリルアミド基、アリル基などが好ましい。
ポリマーは、ポリマーの極性置換基と、極性置換基と対荷電を有する置換基及びエチレン性不飽和結合を有する化合物との塩形成で導入された架橋性基を有してもよいし、上記以外のモノマー、好ましくは親水性モノマーが更に共重合されていてもよい。
より好ましいものとして、特開2005-125749号公報及び特開2006-188038号公報に記載の支持体表面に吸着可能な吸着性基、親水性基及び架橋性基を有する高分子ポリマーが挙げられる。
下塗り層に用いられるポリマーの重量平均分子量(Mw)は、5,000以上が好ましく、1万~30万がより好ましい。
本発明の平版印刷版原版は、画像記録層の上に保護層(オーバーコート層と呼ばれることもある)を有していてもよい。保護層は酸素遮断により画像形成阻害反応を抑制する機能の他、画像記録層における傷の発生防止及び高照度レーザー露光時のアブレーション防止の機能を有する。
変性ポリビニルアルコールとしてはカルボキシ基又はスルホ基を有する酸変性ポリビニルアルコールが好ましく用いられる。具体的には、特開2005-250216号公報及び特開2006-259137号公報に記載の変性ポリビニルアルコールが挙げられる。
好ましく用いられる無機層状化合物は雲母化合物である。雲母化合物としては、例えば、式:A(B,C)2-5D4O10(OH,F,O)2〔ただし、Aは、K、Na及びCaよりなる群から選ばれた少なくとも1種の元素であり、B及びCは、Fe(II)、Fe(III)、Mn、Al、Mg及びVよりなる群から選ばれた少なくとも1種の元素であり、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が挙げられる。
本発明の平版印刷版原版の支持体は、公知の平版印刷版原版用支持体から適宜選択して用いることができる。支持体としては、公知の方法で粗面化処理され、陽極酸化処理されたアルミニウム板が好ましい。
アルミニウム板は更に必要に応じて、特開2001-253181号公報及び特開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、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による表面親水化処理、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ってもよい。
支持体は、中心線平均粗さが0.10~1.2μmであることが好ましい。
本発明の平版印刷版の作製方法は、本発明の平版印刷版原版を画像露光する工程(露光工程)、及び、画像様露光後の平版印刷版原版を印刷機上で印刷インキ及び湿し水から選ばれる少なくとも1つにより、画像記録層の未露光部を除去する工程(機上現像工程)を含むことが好ましい。
また、本発明の平版印刷版の作製方法は、本発明の平版印刷版原版を画像露光する工程(露光工程)、及び、画像露光後の平版印刷版原版をpHが2~11の現像液により画像記録層の未露光部を除去する工程(現像処理工程)を含むことが好ましい。
画像露光は、デジタルデータを赤外線レーザー等により走査露光する方法により行うことが好ましい。
露光光源の波長は、750~1,400nmが好ましく用いられる。750~1,400nmの光源としては、赤外線を放射する固体レーザー及び半導体レーザーが好適である。露光機構は内面ドラム方式、外面ドラム方式、フラットベッド方式等のいずれでもよい。
露光工程はプレートセッターなどにより公知の方法で行うことができる。また、機上現像工程を含む場合には、露光装置を備えた印刷機を用いて、平版印刷版原版を印刷機に装着した後、印刷機上で露光を行ってもよい。
機上現像工程においては、画像露光後の平版印刷版原版に何らの現像処理を施すことなく、印刷機上において、印刷インキ及び湿し水から選ばれた少なくとも一方、好ましくは印刷インキ及び湿し水を供給して印刷(機上現像)を開始すると、印刷途上の初期の段階で平版印刷版原版の未露光部分が除去され、それに伴って親水性支持体表面が露出し非画像部が形成される。印刷インキ及び湿し水としては、公知の平版印刷用の印刷インキ及び湿し水が用いられる。最初に平版印刷版原版表面に供給されるのは、印刷インキでも湿し水でもよいが、湿し水が除去された画像記録層成分によって汚染されることを防止する点で、最初に印刷インキを供給することが好ましい。
このようにして、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。
本発明の平版印刷版原版は、画像記録層の構成成分であるバインダーポリマー等を適宜選択することにより、現像液を用いる現像処理によっても平版印刷版を作製することができる。現像液を用いる現像処理は、アルカリ剤を含むpH14以下の高pHの現像液を用いる態様(アルカリ現像処理ともいう)、並びに、界面活性剤及び水溶性高分子化合物よりなる群から選ばれた少なくとも1種の化合物を含有してもよいpH2~11の現像液を用いる態様(簡易現像処理ともいう)を含む。
また、現像液中に、必要に応じて、水溶性高分子化合物を含有させることにより、現像及びガム液処理工程を同時に行うこともできる。従って後水洗工程は特に必要とせず、1液1工程で現像とガム液処理を行ったのち、乾燥工程を行うこともできる。それ故、現像液を用いる現像処理としては、画像露光後の平版印刷版原版をpHが2~11の現像液により現像処理する工程を含む平版印刷版の作製方法が好ましい。現像処理の後、スクイズローラーを用いて余剰の現像液を除去してから乾燥を行うことが好ましい。
1液1工程で現像とガム液処理を行うとは、現像処理と、ガム液処理とを別々の工程として行うのではなく、現像液に、水溶性高分子化合物を含有させ、1液により、現像処理とガム液処理とを1工程において行うことを意味する。
回転ブラシロールは2本以上が好ましい。更に自動現像処理機は現像処理手段の後に、スクイズローラー等の余剰の現像液を除去する手段や、温風装置等の乾燥手段を備えていることが好ましい。また、自動現像処理機は現像処理手段の前に、画像露光後の平版印刷版原版を加熱処理するための前加熱手段を備えていてもよい。
このような自動現像処理機での処理は、いわゆる機上現像処理の場合に生ずる保護層/感光層に由来の現像カスへの対応から開放されるという利点がある。
アルカリ現像処理においては、前水洗工程により保護層を除去し、次いで高pHのアルカリ性現像液により現像を行い、その後、後水洗工程でアルカリを除去し、ガム引き工程でガム処理を行い、乾燥工程で乾燥する。
簡易現像処理においては、現像及びガム引きを1液で同時に行うことができる。従って、後水洗工程及びガム処理工程は省略することが可能となり、1液で現像とガム引き(ガム液処理)とを行った後、必要に応じて乾燥工程を行うことが好ましい。
更に、前水洗工程も行うことなく、保護層の除去、現像及びガム引きを1液で同時に行うことが好ましい。また、現像及びガム引きの後に、スクイズローラーを用いて余剰の現像液を除去した後、乾燥を行うことが好ましい。
浸漬は、現像液が溜まった現像液槽中に露光済みの平版印刷版原版をくぐらせてもよいし、露光済みの平版印刷版原版の版面上にスプレーなどから現像液を吹き付けてもよい。
なお、現像液に2回以上浸漬する場合であっても、同じ現像液、又は、現像液と現像処理により画像記録層の成分の溶解又は分散した現像液(疲労液)とを用いて2回以上浸漬する場合は、1液での現像処理(1液処理)という。
現像処理は、常法に従って、好ましくは0℃~60℃、より好ましくは15℃~40℃の温度で、例えば、露光処理した平版印刷版原版を現像液に浸漬してブラシで擦る、又は、外部のタンクに仕込んだ処理液をポンプで汲み上げてスプレーノズルから吹き付けてブラシで擦る等により行うことができる。これらの現像処理は、複数回続けて行うこともできる。例えば、外部のタンクに仕込んだ現像液をポンプで汲み上げてスプレーノズルから吹き付けてブラシで擦った後に、再度スプレーノズルから現像液を吹き付けてブラシで擦る等により行うことができる。自動現像機を用いて現像処理を行う場合、処理量の増大により現像液が疲労してくるので、補充液又は新鮮な現像液を用いて処理能力を回復させることが好ましい。
現像液のpHは、2~11が好ましく、5~9がより好ましく、7~9が更に好ましい。現像性や画像記録層の分散性の観点から言えば、pHの値を高めに設定するほうが有利であるが、印刷性、とりわけ汚れの抑制に関しては、pHの値を低めに設定するほうが有効である。
ここで、pHはpHメーター(型番:HM-31、東亜DKK社製)を用いて25℃で測定される値である。
現像液には、アニオン性界面活性剤、ノニオン性界面活性剤、カチオン性界面活性剤、両性界面活性剤などの界面活性剤を含有することができる。
上記現像液は、ブラン汚れ性の観点から、アニオン性界面活性剤及び両性界面活性剤よりなる群から選ばれた少なくとも1種を含むことが好ましい。
また、上記現像液は、ノニオン性界面活性剤を含むことが好ましく、ノニオン性界面活性剤と、アニオン性界面活性剤及び両性界面活性剤よりなる群から選ばれた少なくとも1種と、を含むことがより好ましい。
R1-Y1-X1 (I)
式(I)中、R1は置換基を有していてもよい、アルキル基、シクロアルキル基、アルケニル基、アラルキル基又はアリール基を表す。
アルキル基としては、例えば、炭素数1~20のアルキル基が好ましく、具体的には、メチル基、エチル基、プロピル基、n-ブチル基、sec-ブチル基、ヘキシル基、2-エチルヘキシル基、オクチル基、デシル基、ドデシル基、ヘキサデシル基、ステアリル基等を好ましく挙げることができる。
シクロアルキル基としては、単環型でもよく、多環型でもよい。単環型としては、炭素数3~8の単環型シクロアルキル基であることが好ましく、シクロプロピル基、シクロペンチル基、シクロヘキシル基又はシクロオクチル基であることがより好ましい。多環型としては例えば、アダマンチル基、ノルボルニル基、イソボロニル基、カンファニル基、ジシクロペンチル基、α-ピネル基、トリシクロデカニル基等を好ましく挙げることができる。
アルケニル基としては、例えば、炭素数2~20のアルケニル基であることが好ましく、具体的には、ビニル基、アリル基、ブテニル基、シクロヘキセニル基等を好ましく挙げることができる。
アラルキル基としては、例えば、炭素数7~12のアラルキル基であることが好ましく、具体的には、ベンジル基、フェネチル基、ナフチルメチル基等を好ましく挙げることができる。
アリール基としては、例えば、炭素数6~15のアリール基であることが好ましく、具体的には、フェニル基、トリル基、ジメチルフェニル基、2,4,6-トリメチルフェニル基、ナフチル基、アントリル基、9,10-ジメトキシアントリル基等を好ましく挙げることができる。
Y1は、単結合、-CnH2n-、-Cn-mH2(n-m)OCmH2m-、-O-(CH2CH2O)n-、-O-(CH2CH2CH2O)n-、-CO-NH-、又は、これらの2以上の組み合わせからなる2価の連結基を表し、n≧1及びn≧m≧0を満たす。
式(I-A)又は式(I-B)で表される化合物におけるXA1及びXA2は、スルホン酸塩基、又は、カルボン酸塩基であることが好ましい。また、XA1及びXA2における塩構造は、アルカリ金属塩が特に水系溶媒への溶解性が良好であり好ましい。中でも、ナトリウム塩、又は、カリウム塩が特に好ましい。
上記式(I-A)又は式(I-B)で表される化合物としては、特開2007-206348号公報の段落0019~0037の記載を参照することができる。
アニオン性界面活性剤としては、特開2006-65321号公報の段落0023~0028に記載の化合物も好適に用いることができる。
R2、R3、R12及びR13は、各々独立に、水素原子、アルキル基又はエチレンオキサイド基を含有する基を表す。
R4及びR14は、各々独立に、単結合又はアルキレン基を表す。
また、R1、R2、R3及びR4のうち2つの基は互いに結合して環構造を形成してもよく、R11、R12、R13及びR14のうち2つの基は互いに結合して環構造を形成してもよい。
R3又はR13で表されるエチレンオキサイドを含有する基としては、-Ra(CH2CH2O)nRbで表される基を挙げることができる。ここで、Raは単結合、酸素原子又は2価の有機基(好ましくは炭素数10以下)を表し、Rbは水素原子又は有機基(好ましくは炭素数10以下)を表し、nは1~10の整数を表す。
一般式(1)で表される化合物又は一般式(2)で表される化合物は、アミド結合を有することが好ましく、R1又はR11の連結基としてアミド結合を有することがより好ましい。
一般式(1)で表される化合物又は一般式(2)で表される化合物の代表的な例を以下に示すが、本発明はこれらに限定されるものではない。
両性イオン系界面活性剤は現像液中に、1種単独で用いてもよいし、2種類以上を組み合わせて使用してもよい。
また、アセチレングリコール系とアセチレンアルコール系のオキシエチレン付加物、フッ素系等の界面活性剤も同様に使用することができる。これら界面活性剤は2種以上併用することもできる。
XN-YN-O-(A1)nB-(A2)mB-H (N1)
式中、XNは置換基を有していてもよい芳香族基を表し、YNは単結合又は炭素原子数1~10のアルキレン基を表し、A1及びA2は互いに異なる基であって、-CH2CH2O-又は-CH2CH(CH3)O-のいずれかを表し、nB及びmBはそれぞれ独立に、0~100の整数を表し、ただし、nBとmBとは同時に0ではなく、また、nB及びmBのいずれかが0である場合には、nB及びmBは1ではない。
式中、XNの芳香族基としてフェニル基、ナフチル基、アントラニル基などが挙げられる。これらの芳香族基は置換基を有していてもよい。置換基としては、炭素数1~100の有機基が挙げられる。なお、式中、A及びBがともに存在するとき、ランダムでもブロックの共重合体でもよい。
また、ノニオン性界面活性剤としては、特開2006-65321号公報の段落0030~0040に記載された化合物も好適に用いることができる。
界面活性剤の含有量は、現像液の全質量に対し、1質量%~25質量%が好ましく、2質量%~20質量%がより好ましく、3質量%~15質量%が更に好ましく、5質量%~10質量%が特に好ましい。上記範囲であると、耐キズ汚れ性により優れ、現像カスの分散性に優れ、また、得られる平版印刷版のインキ着肉性に優れる。
現像液は、現像液の粘度調整及び得られる平版印刷版の版面の保護の観点から、水溶性高分子を含むことができる。
水溶性高分子としては、大豆多糖類、変性澱粉、アラビアガム、デキストリン、繊維素誘導体(例えば、カルボキシメチルセルロース、カルボキシエチルセルロース、メチルセルロース等)及びその変性体、プルラン、ポリビニルアルコール及びその誘導体、ポリビニルピロリドン、ポリアクリルアミド及びアクリルアミド共重合体、ビニルメチルエーテル/無水マレイン酸共重合体、酢酸ビニル/無水マレイン酸共重合体、スチレン/無水マレイン酸共重合体などの水溶性高分子化合物を含有することができる。
現像液は、水溶性高分子化合物を含まないか、又は、水溶性高分子化合物の含有量は、現像液の全質量に対し、0質量%を超え1質量%以下であることが好ましく、水溶性高分子化合物を含まないか、又は、水溶性高分子化合物の含有量は、現像液の全質量に対し、0質量%を超え0.1質量%以下であることがより好ましく、水溶性高分子化合物を含まないか、又は、水溶性高分子化合物の含有量は、現像液の全質量に対し、0質量%を超え0.05質量%以下であることが更に好ましく、水溶性高分子化合物を含有しないことが特に好ましい。上記態様であると、現像液の粘度が適度であり、自動現像機のローラー部材に現像カス等が堆積することを抑制することができる。
本発明に用いられる現像液は、上記の他に、湿潤剤、防腐剤、キレート化合物、消泡剤、有機酸、有機溶剤、無機酸、無機塩などを含有することができる。
防腐剤の添加量は、細菌、カビ、酵母等に対して、安定に効力を発揮する量であって、細菌、カビ、酵母の種類によっても異なるが、現像液の全質量に対し、0.01質量%~4質量%の範囲が好ましい。また、種々のカビ、殺菌に対して効力のあるように2種以上の防腐剤を併用することが好ましい。
キレート剤は、処理液組成中に安定に存在し、印刷性を阻害しないものであることが好ましい。キレート剤の含有量は、現像液の全質量に対し、0.001質量%~1.0質量%であることが好ましい。
なお、シリコーン系界面活性剤は、消泡剤と見なすものとする。
消泡剤の含有量は、現像液の全質量に対し、0.001質量%~1.0質量%の範囲が好適である。
現像液は、水性の現像液であることが好ましい。
アルコール化合物としては、メタノール、エタノール、プロパノール、イソプロパノール、ベンジルアルコール等が挙げられる。中でも、ベンジルアルコールが好ましい。
アルコール化合物の含有量は、現像カスの分散性の観点から、現像液の全質量に対し、0.01~5質量%が好ましく、0.1~2質量%がより好ましく、0.2~1質量%が特に好ましい。
中間体SM-5の合成スキームを以下に示す。
中間体SM-6の合成スキームを以下に示す。
反応終了後、水を1600ml添加し、室温で1時間撹拌した。その後、析出した固体をろ過により回収し、蒸留水1000gで洗浄後、50℃設定の送風乾燥機にて8時間乾燥することで、中間体SM-6が317.4g(0.57mol)得られた。
化合物1の合成スキームを以下に示す。
1H-NMR(400MHz、重ジメチルスルホキシド)δ= 1.10(s,12H)、1.83-1.94(m,4H)、2.30(s,6H)、2.88(s,4H)、3.20(s,6H)、3.29-3.33(m,4H)、4.04(t,4H)、5.84(d,2H)、7.06-7.16(m,6H)、7.18-7.25(m,6H)、7.37-7.47(m,8H)、7.56(d,2H)、7.74(s,1H)、7.77(s,1H)
化合物2の合成スキームを以下に示す。
得られた化合物2の構造は、NMRにて同定した。同定結果を以下に示す。
1H-NMR(400MHz、重ジメチルスルホキシド)δ= 0.85(m,3H)、1.17-1.4(m,10H)、1.67(m,2H)、3.16(d,4H)、3.85(s,3H)、3.90-4.00(m,8H)、4.10(q,4H)、6.44(s,2H)、6.98(d,2H)、7.39(m,2H)、7.55(m,2H)、7.76(d,2H)、7.82(d,2H)
〔平版印刷版原版Aの作製〕
厚さ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。その後、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板表面を砂目立てし、水でよく洗浄した。アルミニウム板を45℃の25質量%水酸化ナトリウム水溶液に9秒間浸漬してエッチングを行い、水洗後、さらに60℃で20質量%硝酸水溶液に20秒間浸漬し、水洗した。砂目立て表面のエッチング量は約3g/m2であった。
次に、アルミニウム板に15質量%硫酸水溶液(アルミニウムイオンを0.5質量%含む)を電解液として電流密度15A/dm2で2.5g/m2の直流陽極酸化皮膜を形成し、水洗、乾燥して支持体Aを作製した。陽極酸化皮膜の表層における平均ポア径(表面平均ポア径)は10nmであった。
陽極酸化皮膜の表層におけるポア径の測定は、超高分解能型SEM((株)日立製作所製S-900)を使用し、12Vという比較的低加速電圧で、導電性を付与する蒸着処理等を施すこと無しに、表面を15万倍の倍率で観察し、50個のポアを無作為抽出して平均値を求める方法で行った。標準偏差誤差は±10%以下であった。
上記支持体A上に、下記組成の下塗り層塗布液(1)を乾燥塗布量が20mg/m2になるよう塗布して下塗り層を形成した。
・ポリマー(P-1)〔下記〕:0.18g
・ヒドロキシエチルイミノ二酢酸:0.10g
・水:61.4g
3つ口フラスコに、アンカミン 1922A(ジエチレングリコールジ(アミノプロピル)エーテル、エアープロダクツ社製)200部、蒸留水435部及びメタノール410部を加え、5℃まで冷却した。次に安息香酸222.5部及び4-ヒドロキシ-2,2,6,6-テトラメチルピペリジン-1-オキシル(4-OH-TEMPO)0.025部を加え、メタクリル酸無水物280部を、反応液の内温が10℃以下となる様に滴下した。反応液を5℃で6時間撹拌し、次いで25℃にて12時間撹拌した後、リン酸70部を加えpHを3.3に調整した。反応液をステンレスビーカーに移し、酢酸エチル3,320部、メチル-tertブチルエーテル(MTBE)1,120部及び蒸留水650部を加え、激しく撹拌した後静置した。上層(有機層)を廃棄した後、酢酸エチル1,610部1.8Lを加え、激しく撹拌した後静置し、上層を廃棄した。更に、酢酸エチル1,350部を加え、激しく撹拌した後静置し、上層を廃棄した。次いで、MTBE1,190部を加え、激しく撹拌した後静置し、上層を廃棄した。得られた水溶液に4-OH-TEMPO0.063部を加えてモノマーM-1の水溶液(固形分換算20.1質量%)を12,000部得た。
ライトエステル P-1M(2-メタクロイロキシエチルアシッドホスフェート、共栄社化学(株)製)420部、ジエチレングリコールジブチルエーテル1,050部及び蒸留水1,050部を分液ロートに加え、激しく撹拌した後静置した。上層を廃棄した後、ジエチレングリコールジブチルエーテル1,050部を加え、激しく撹拌した後静置した。上層を廃棄してモノマーM-2の水溶液(固形分換算10.5質量%)を13,000部得た。
三口フラスコに、蒸留水を600.6部、モノマーM-1水溶液を33.1部及び下記モノマーM-3を46.1部加え、窒素雰囲気下で55℃に昇温した。次に、下記滴下液1を2時間掛けて滴下し、30分撹拌した後、VA-046B(和光純薬工業(株)製)3.9部を加え、80℃に昇温し、1.5時間撹拌した。反応液を室温(25℃、以下同様)に戻した後、30質量%水酸化ナトリウム水溶液175部を加え、pHを8.3に調整した。次に、4-OH-TEMPO0.152部を加え、53℃に昇温した。メタクリル酸無水物66.0部を加えて53℃で3時間撹拌した。室温に戻した後、反応液をステンレスビーカーに移し、MTBE1,800部を加え、激しく撹拌した後静置し、上層を廃棄した。同様にしてMTBE1,800部による洗浄操作を更に2回繰り返した後、得られた水層に蒸留水1,700部及び4-OH-TEMPOを0.212部加え、均一溶液としてポリマーP-1(固形分換算11.0%)を41,000部得た。ゲル浸透クロマトグラフィー(GPC)法によるポリエチレングリコール換算値とした重量平均分子量(Mw)は20万であった。
・上記モノマーM-1水溶液:132.4g
・上記モノマーM-2水溶液:376.9g
・モノマーM-3〔下記〕:184.3g
・ブレンマー PME4000(日油(株)製):15.3g
・VA-046B(和光純薬工業(株)製):3.9g
・蒸留水:717.4g
VA-046B:2,2’-アゾビス[2-(2-イミダゾリン-2-イル)プロパン]ジスルフェートジハイドレート
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、100℃で60秒間オーブン乾燥して乾燥塗布量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)及びミクロゲル液を塗布直前に混合し撹拌することにより調製した。
・バインダーポリマー(1)〔下記〕 0.240g
・赤外線吸収剤(D-1) 〔下記〕 0.024g
・表1記載の特定化合物又は公知の化合物(重合開始剤) 0.245g
・重合性化合物 0.192g
トリス(アクリロイルオキシエチル)イソシアヌレート
(NKエステル A-9300、新中村化学(株)製)
・低分子親水性化合物 0.062g
トリス(2-ヒドロキシエチル)イソシアヌレート
・フッ素系界面活性剤(1)〔下記〕 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
<多価イソシアネート化合物(1)の調製>
イソホロンジイソシアネート17.78g(80mmol)と下記多価フェノール化合物(1)7.35g(20mmol)との酢酸エチル(25.31g)懸濁溶液に、ビスマストリス(2-エチルヘキサノエート)(ネオスタン U-600、日東化成(株)製)43mgを加えて撹拌した。発熱が収まった時点で反応温度を50℃に設定し、3時間撹拌して多価イソシアネート化合物(1)の酢酸エチル溶液(50質量%)を得た。
下記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12000rpmで10分間乳化した。得られた乳化物を45℃で4時間撹拌後、1,8-ジアザビシクロ[5.4.0]ウンデカ-7-エン-オクチル酸塩(U-CAT SA102、サンアプロ(株)製)の10質量%水溶液5.20gを加え、室温で30分撹拌し、45℃で24時間静置した。蒸留水で、固形分濃度を20質量%になるように調整し、ミクロゲル(1)の水分散液を得た。動的光散乱式粒径分布測定装置 LB-500((株)堀場製作所製)を用いて、光散乱法により体積平均粒径を測定したところ、0.28μmであった。
(成分1)酢酸エチル:12.0g
(成分2)トリメチロールプロパン(6モル)とキシレンジイソシアネート(18モル)を付加させ、これにメチル片末端ポリオキシエチレン(1モル、オキシエチレン単位の繰返し数:90)を付加させた付加体(50質量%酢酸エチル溶液、三井化学(株)製):3.76g
(成分3)多価イソシアネート化合物(1)(50質量%酢酸エチル溶液として):15.0g
(成分4)ジペンタエリスリトールペンタアクリレート(SR-399、サートマー社製)の65質量%酢酸エチル溶液:11.54g
(成分5)スルホン酸塩型界面活性剤(パイオニンA-41-C、竹本油脂(株)製)の10%酢酸エチル溶液:4.42g
上記各平版印刷版原版Aについて、機上現像性、熱経時安定性(1)、及び耐刷性を以下の評価方法により評価した。評価結果を表1に示す。
<機上現像性>
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により、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。
露光された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Values-G(N)墨インキ(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、毎時10,000枚の印刷速度で、特菱アート紙(76.5kg)(三菱製紙(株)製)に100枚印刷を行った。
印刷機上で画像記録層の未露光部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計測し、機上現像性として評価した。枚数が少ない程、機上現像性が良好である。
平版印刷版原版を25℃、60%の環境下で1時間調湿した後、梱包した。次に、梱包物を60℃で4日間熱経時した。熱経時終了後、上記機上現像性の評価と同様にして、画像露光及び機上現像を行い印刷用紙の枚数を計測し、熱経時安定性(1)を評価した。枚数が少ない程、熱経時安定性が良好である。
上記機上現像性の評価を行った後、さらに印刷を続けた。印刷枚数の増加に伴い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測定した値が印刷100枚目の測定値よりも5%低下するまでの印刷枚数を計測した。耐刷性は、下記式に示すように、印刷枚数が5万枚の場合を100とする相対耐刷性により評価した。数値が大きい程、耐刷性が良好である。
相対耐刷性=((対象平版印刷版原版の印刷枚数)/50,000) × 100
公知の化合物を重合開始剤として含有する比較例の平版印刷版原版は、熱経時安定性(1)、機上現像性、及び耐刷性のいずれか1つ以上において劣っている。
〔平版印刷版原版Bの作製〕
上記平版印刷版原版Aの作製において、上記支持体Aの代りに上記支持体Bを用い、上記画像記録層塗布液(1)の代りに、下記画像記録層塗布液(2)を用い、更に、画像記録層上に下記保護層を形成する他は上記平版印刷版原版Aの作製と同様にして、平版印刷版原版Bを作製した。画像記録層塗布液(2)は下記感光液(2)及びミクロゲル液を塗布直前に混合し撹拌することにより調製した。各平版印刷版原版の作製において使用した画像記録層塗布液(2)中の赤外線吸収剤、特定化合物、重合開始剤を表2にまとめて記載する。
・バインダーポリマー(1)〔上記〕: 0.240g
・赤外線吸収剤(D-1)〔上記〕又は(D-2)〔下記〕 0.024g
・表2記載の特定化合物(重合開始剤)又は公知の重合開始剤、又はパラメータ規定化合物 表2記載の量
・表2記載の特定化合物(非オニウム塩型) 表2記載の量
・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
・酸発色剤:2’-アニリノ-6’-(N-エチル-N-イソペンチルアミノ)-3’-メチルスピロ[フタリド-3,9’-キサンテン](S-205、福井山田化学工業(株)製) 0.080g
・フッ素系界面活性剤(1)〔上記〕: 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)〔上記〕: 2.640g
・蒸留水: 2.425g
上記感光液(2)に用いた赤外線吸収剤(D-2)の構造を以下に示す。なお、赤外線吸収剤(D-2)は、上記の化合物1である。
画像記録層上に、下記組成の保護層塗布液をバー塗布し、120℃で60秒間オーブン乾燥して、乾燥塗布量が0.15g/m2の保護層を形成した。
・無機層状化合物分散液(1)〔下記〕 1.5g
・ポリビニルアルコール(CKS50、日本合成化学工業(株)製、
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(PVA-405、(株)クラレ製、
けん化度81.5モル%、重合度500)6質量%水溶液 0.03g
・界面活性剤(ポリオキシエチレンラウリルエーテル、エマレックス710、日本エマルジョン(株)製)1質量%水溶液 0.86g
・イオン交換水 6.0g
<無機層状化合物分散液(1)の調製>
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。
上記各平版印刷版原版Bについて、平版印刷版原版Aにおけると同様に、機上現像性、熱経時安定性(1)、及び耐刷性を評価した。更に、発色性、及び熱経時安定性(2)(リング状発色防止性)を以下の評価方法により評価した。結果を表2に示す。
平版印刷版原版を、水冷式40W赤外線半導体レーザー搭載のCreo社製Trendsetter3244VXにより、出力11.7W、外面ドラム回転数250rpm、解像度2,400dpi(dot per inch、1inch=25.4mm)の条件で露光した。露光は25℃、50%RHの環境下で行った。
露光直後、平版印刷版原版の発色を測定した。測定は、コニカミノルタ(株)製分光測色計CM2600dとオペレーションソフトCM-S100Wとを用い、SCE(正反射光除去)方式で行った。発色性は、L*a*b*表色系のL*値(明度)を用い、露光部のL*値と未露光部のL*値との差ΔLにより評価した。表2には、ΔLの数値を記載した。ΔLの値が大きい程、発色性が優れ、発色による平版印刷版の検版性にも優れる。
平版印刷版原版を25℃、60%の環境下で1時間調湿した後、梱包した。次に、梱包物を60℃で4日間熱経時した。熱経時終了後、50×300mmの面積範囲にて、リング状に発色している点を目視で数えた。発色点の数がゼロのものをA、1~10のものをB、10より大きいものをCとしてリング状発色防止性を評価した。平版印刷版原版としては、リング状発色がないことが求められる(B、Cはリング状発色の程度差を表わすための指標)。
公知の重合開始剤を含有する比較例の平版印刷版原版は、熱経時安定性(1)、機上現像性、発色性、及び熱経時安定性(2)のいずれか1つ以上において劣っている。
〔平版印刷版原版Cの作製〕
・赤外線吸収剤(D-3)又は(D-4) 0.018g
・表3記載の特定化合物(重合開始剤)又は公知の重合開始剤、又はパラメータ規定化合物 表3記載の量
・表3記載の特定化合物(非オニウム塩型) 表3記載の量
・ボレート化合物: 0.010g
TPB〔下記〕
・ポリマー粒子水分散液(1)(22質量%)〔下記〕: 10.0g
・重合性化合物: 1.50g
SR-399(サートマー社製)
・酸発色剤:2’-アニリノ-6’-(N-エチル-N-イソペンチルアミノ)-3’-メチルスピロ[フタリド-3,9’-キサンテン](S-205、福井山田化学工業(株)製) 0.080g
・メルカプト-3-トリアゾール: 0.2g
・Byk 336(Byk Chemie社製): 0.4g
・Klucel M(Hercules社製): 4.8g
・ELVACITE 4026(Ineos Acrylics社製):
2.5g
・n-プロパノール: 55.0g
・2-ブタノン: 17.0g
・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)
<ポリマー粒子水分散液(1)の調製>
4つ口フラスコに撹拌機、温度計、滴下ロート、窒素導入管、還流冷却器を施し、窒素ガスを導入して脱酸素を行いつつ、ポリエチレングリコールメチルエーテルメタクリレート(PEGMA、エチレングリコールの平均繰返し単位数:50)10g、蒸留水200g及びn-プロパノール200gを加えて内温が70℃となるまで加熱した。次に、予め混合されたスチレン(St)10g、アクリロニトリル(AN)80g及び2,2’-アゾビスイソブチロニトリル0.8gの混合物を1時間かけて滴下した。滴下終了後5時間そのまま反応を続けた後、2,2’-アゾビスイソブチロニトリル0.4gを添加し、内温を80℃まで上昇させた。続いて、0.5gの2,2’-アゾビスイソブチロニトリルを6時間かけて添加した。合計で20時間反応させた段階でポリマー化はモル基準で98%以上進行しており、質量比でPEGMA/St/AN=10/10/80のポリマー粒子水分散液(1)を調製した。ポリマー粒子の粒径分布は、粒径150nmに極大値を有していた。
上記各平版印刷版原版Cについて、平版印刷版原版Bにおけると同様に、熱経時安定性(1)、機上現像性、耐刷性、発色性、及び熱経時安定性(2)を評価した。評価結果を表3に示す。
公知の重合開始剤を含有する比較例の平版印刷版原版は、熱経時安定性(1)、機上現像性、発色性、及び熱経時安定性(2)のいずれか1つ以上において劣っている。
〔平版印刷版原版Dの作製〕
・赤外線吸収剤(D-3)、(D-5)又は(D-6) 0.045g/m2
・表4記載の特定化合物(酸発生剤)又は公知の酸発生剤、又はパラメータ規定化合物 表4記載
・表4記載の特定化合物(非オニウム塩型) 表4記載
・ボレート化合物: 0.010g/m2
TPB〔上記〕
・酸発色剤:2’-アニリノ-6’-(N-エチル-N-イソペンチルアミノ)-3’-メチルスピロ[フタリド-3,9’-キサンテン](S-205、福井山田化学工業(株)製) 0.080g/m2
・ポリマー粒子水分散液(2): 0.693g/m2
・Glascol E15: 0.09g/m2
(Allied Colloids Manufacturing 社製)
・ERKOL WX48/20 (ERKOL社製):0.09g/m2
・Zonyl FSO100 (DuPont社製):0.0075g/m2
・Glascol E15:ポリアクリル酸
・ERKOL WX48/20:ポリビニルアルコール/ポリ酢酸ビニル共重合体
・Zonyl FSO100:界面活性剤
・ポリマー粒子水分散液(2):アニオン性湿潤剤で安定化されたスチレン/アクリロニトリル共重合体(モル比50/50、平均粒径61nm、固形分約20%)
上記各平版印刷版原版Dについて、平版印刷版原版Bにおけると同様に、熱経時安定性(1)、機上現像性、耐刷性、発色性、及び熱経時安定性(2)を評価した。評価結果を表4に示す。
公知の酸発生剤を含有する比較例の平版印刷版原版は、熱経時安定性(1)、機上現像性、発色性、及び熱経時安定性(2)のいずれか1つ以上において劣っている。
〔平版印刷版原版Eの作製〕
厚さ0.3mmのアルミニウム板(材質JIS A 1050)に、以下の(a)~(i)の各処理を連続的に施して表面処理を行った。なお、各処理および水洗の後にはニップローラで液切りを行った。
上記アルミニウム板に、カセイソーダ濃度2.6質量%、アルミニウムイオン濃度6.5質量%、温度70℃の水溶液を用いてスプレーによるエッチング処理を行い、アルミニウム板を6g/m2溶解した。その後、スプレーによる水洗を行った。
アルミニウム板に、温度30℃の硝酸濃度1質量%水溶液(アルミニウムイオンを0.5質量%含む。)を用いて、スプレーによるデスマット処理を行い、その後、スプレーで水洗した。デスマット処理に用いた硝酸水溶液は、硝酸水溶液中で交流を用いて電気化学的粗面化処理を行う工程の廃液を用いた。
60Hzの交流電圧を用いて連続的に電気化学的粗面化処理を行った。電解液は、硝酸10.5g/L水溶液(アルミニウムイオンを5g/L、アンモニウムイオンを0.007質量%含む)、液温50℃であった。交流電源波形は、電流値がゼロからピークに達するまでの時間TPが0.8msec、duty比1:1、台形の矩形波交流を用いて、カーボン電極を対極として電気化学的粗面化処理を行った。補助アノードにはフェライトを用いた。電流密度は電流のピーク値で30A/dm2、電気量はアルミニウム板が陽極時の電気量の総和で220C/dm2であった。補助陽極には電源から流れる電流の5%を分流させた。その後、スプレーによる水洗を行った。
アルミニウム板に、カセイソーダ濃度26質量%、アルミニウムイオン濃度6.5質量%の水溶液を用いてスプレーによるエッチング処理を32℃で行い、アルミニウム板を0.25g/m2溶解し、上記電気化学的粗面化処理を行ったときに生成した水酸化アルミニウムを主体とするスマット成分を除去し、また、生成したピットのエッジ部分を溶解してエッジ部分を滑らかにした。その後、スプレーによる水洗を行った。
温度30℃の硫酸濃度15質量%水溶液(アルミニウムイオンを4.5質量%含む)を用いて、スプレーによるデスマット処理を行い、その後、スプレーで水洗した。デスマット処理に用いた硝酸水溶液は、硝酸水溶液中で交流を用いて電気化学的粗面化処理を行う工程の廃液を用いた。
60Hzの交流電圧を用いて連続的に電気化学的粗面化処理を行った。電解液は、塩酸2.5g/L水溶液(アルミニウムイオンを5g/L含む)、温度35℃であった。交流電源波形は、電流値がゼロからピークに達するまでの時間TPが0.8msec、duty比1:1、台形の矩形波交流を用いて、カーボン電極を対極として電気化学的粗面化処理を行った。補助アノードにはフェライトを用いた。電流密度は電流のピーク値で25A/dm2、電気量はアルミニウム板が陽極時の電気量の総和で50C/dm2であった。その後、スプレーによる水洗を行った。
アルミニウム板に、カセイソーダ濃度26質量%、アルミニウムイオン濃度6.5質量%の水溶液を用いてスプレーによるエッチング処理を32℃で行い、アルミニウム板を0.1g/m2溶解し、上記電気化学的粗面化処理を行ったときに生成した水酸化アルミニウムを主体とするスマット成分を除去し、また、生成したピットのエッジ部分を溶解してエッジ部分を滑らかにした。その後、スプレーによる水洗を行った。
アルミニウム板に15質量%硫酸水溶液(アルミニウムイオンを0.5質量%含む)を電解液として電流密度15A/dm2で2.5g/m2の直流陽極酸化皮膜を形成し、水洗、乾燥した。陽極酸化皮膜の表層における平均ポア径(表面平均ポア径)は10nmであった。
陽極酸化皮膜の表層におけるポア径の測定は、超高分解能型SEM((株)日立製作所製S-900)を使用し、12Vという比較的低加速電圧で、導電性を付与する蒸着処理等を施すこと無しに、表面を15万倍の倍率で観察し、50個のポアを無作為抽出して平均値を求める方法で行った。標準偏差誤差は±10%以下であった。
非画像部の親水性を確保するため、アルミニウム板に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た後、水洗して支持体Eを作製した。Siの付着量は9.5mg/m2であった。支持体E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、0.27μmであった。
上記支持体E上に、下記組成の下塗り層塗布液(2)を乾燥塗布量が20mg/m2になるよう塗布して下塗り層を形成した。
・ポリマー(P-2)[下記] 0.18g
・エチレンジアミン四酢酸4ナトリウム 0.10g
・ポリオキシエチレンラウリルエーテル 0.03g
・水 61.39g
下塗り層上に、下記組成の画像記録層塗布液(5)をバー塗布した後、100℃で60秒でオーブン乾燥して、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(5)は下記感光液(5)およびミクロゲル液を塗布直前に混合し攪拌することにより調製した。
・バインダーポリマー(2)〔下記構造〕: 0.240g
・赤外線吸収剤(D-2)〔上記〕 0.024g
・表5記載の特定化合物(重合開始剤)又は公知の重合開始剤
0.245g
・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
・着色剤〔下記〕: 0.030g
・フッ素系界面活性剤(1)〔上記〕: 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)〔上記〕: 2.640g
・蒸留水: 2.425g
上記画像記録層上に、更に上記保護層塗布液をバー塗布した後、120℃、60秒でオーブン乾燥し、乾燥塗布量0.15g/m2の保護層を形成した。
上記各平版印刷版原版Eについて、耐刷性及び熱経時安定性(3)を、以下の評価方法により評価した。評価結果を表5に示す。
[画像露光]
平版印刷版原版を赤外線半導体レーザー搭載の富士フイルム(株)製Luxel PLATESETTER T-6000IIIにて、外面ドラム回転数1000rpm、レーザー出力70%、解像度2400dpiの条件で露光した。露光画像にはベタ画像及び50%網点チャートを含むようにした。[現像処理]
露光後の平版印刷版に、Glunz & Jensen社製のClean Out Unit+ C85を使用し、60cm/minの搬送速度で20℃にて現像処理を行い、平版印刷版を作製した。現像処理には、下記組成の現像液を使用した。この現像液は、保護層の除去、現像及びガム引きを1液で行うことができる現像液である。
・ペレックスNBL(アルキルナフタレンスルホン酸ナトリウム、花王(株)製アニオン界面活性剤): 7.8質量部
・ニューコールB13(ポリオキシエチレンアリールエーテル、日本乳化剤(株)製ノニオン界面活性剤): 2.00質量部
・サーフィノール2502(Air Products社製):
0.6質量部
・ベンジルアルコール(和光純薬工業(株)製): 0.8質量部
・グルコン酸ソーダ(扶桑化学工業(株)製): 3.0質量部
・リン酸一水素二ナトリウム(和光純薬工業(株)製): 0.3質量部
・炭酸水素ナトリウム(和光純薬工業(株)製): 0.3質量部
・消泡剤(Bluester Silicones社製SILCOLAPSE432):
0.01質量部
・水: 85.49質量部
(pH: 8.6)
現像した平版印刷版を(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(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、毎時10,000枚の印刷速度で、特菱アート紙(76.5kg)(三菱製紙(株)製)に印刷を行った。印刷枚数の増加に伴い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測定した値が印刷100枚目の測定値よりも5%低下するまでの印刷枚数を計測した。耐刷性は、下記式に示すように、印刷枚数が5万枚の場合を100とする相対耐刷性により評価した。数値が大きい程、耐刷性が良好である。
相対耐刷性=((対象平版印刷版原版の印刷枚数)/50,000) × 100
平版印刷版原版を25℃、60%の環境下で1時間調湿した後、梱包した。次に、梱包物を60℃で5日間熱経時した。熱経時終了後、上記耐刷性評価と同様にして、画像露光及び現像処理を行い、現像処理後に未露光部の濃度測定を行った。濃度測定は、分光濃度計(X-Rite社SpectroEye)を使用し、シアン濃度を測定した。得られたシアン濃度の値と塗布を実施していない支持体Eのシアン濃度の値との差分(△D)を算出し、熱経時安定性をA~Cで評価した。△Dが小さいほど、現像処理後に非画像部に残る画像記録層が少なく、熱経時安定性がよい。
A:△D≦0.01
B:0.01<△D≦0.03
C:0.03<△D
また、本発明によれば、高い熱経時安定性を有する硬化性組成物を提供することができる。
また、本発明によれば、高い熱経時安定性を有し、機上現像性に優れ、且つ、優れた耐刷性を有する平版印刷版を作製できる平版印刷版原版を提供することができる。
更に、本発明によれば、高い熱経時安定性を有し、検版性及び機上現像性に優れ、且つ、優れた耐刷性を有する平版印刷版を作製できる平版印刷版原版を提供することができる。
更に、本発明によれば、高い熱経時安定性を有し、優れた耐刷性を有する平版印刷版を作製できる平版印刷版原版を提供することができる。
更に、本発明によれば、上記平版印刷版原版を用いる平版印刷版の作製方法、上記平版印刷版原版の画像記録層に用いられる化合物を提供することができる。
本出願は、2017年2月28日出願の日本特許出願(特願2017-37779)、2017年9月29日出願の日本特許出願(特願2017-191496)、及び2017年12月27日出願の日本特許出願(特願2017-252560)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 (25)
- a)ハンセンのSP値パラメータにおけるδdが16以上、δpが16以上32以下、δHがδpの60%以下である有機アニオン、及びb)カウンターカチオンを有する塩化合物を含有する、硬化性組成物。
- 前記有機アニオンが、分子内に芳香環又は複素環を有する有機アニオンである、請求項1に記載の硬化性組成物。
- 前記有機アニオンが、(A)環に結合するスルホンアミドアニオン構造又は環に結合するスルホンイミドアニオン構造を有する有機アニオンである、請求項1に記載の硬化性組成物。
- 前記有機アニオンが、下記式(V)で表される有機アニオンである請求項2に記載の硬化性組成物。
式(V)中、Cy1及びCy2は、同じでも異なってもよく、それぞれ、ホウ素原子、酸素原子及びYと共に形成される環構造を表わし、Yは、それぞれ独立に、-O-又は-NR5-を表し、R5は水素原子、アルキルカルボニル基、アリールカルボニル基、アルキルスルホニル基、アリールスルホニル基、アルコキシカルボニル基、アリール基又はヘテロアリール基を表す。
前記Cy1で表される環構造は、アルキルアミド基、アルケニルアミド基、アリールアミド基、アルキルウレア基、アリールウレア基、スルホンアミド構造を有する基、及びスルホンイミド構造を有する基からなる群より選択される少なくとも一つの基を有する芳香環で縮環されており、前記Cy2で表される環構造は、アルキルアミド基、アルケニルアミド基、アリールアミド基、アルキルウレア基、アリールウレア基、スルホンアミド構造を有する基、及びスルホンイミド構造を有する基からなる群より選択される少なくとも一つの基を有する芳香環で縮環されている。 - 前記有機アニオンが、下記式(VI)で表される有機アニオンである請求項4に記載の硬化性組成物。
式(VI)中、R7~R14は、同じでも異なってもよく、それぞれ独立に、水素原子、アルキル基、アルキルアミド基、アルケニルアミド基、アリールアミド基、アルキルウレア基、アリールウレア基、スルホンアミド構造を有する基、又はスルホンイミド構造を有する基を表す。
R7~R10の少なくとも一つは、アルキルアミド基、アルケニルアミド基、アリールアミド基、アルキルウレア基、アリールウレア基、スルホンアミド構造を有する基、又はスルホンイミド構造を有する基を表し、
R11~R14の少なくとも一つは、アルキルアミド基、アルケニルアミド基、アリールアミド基、アルキルウレア基、アリールウレア基、スルホンアミド構造を有する基、又はスルホンイミド構造を有する基を表す。 - (A)環に結合するスルホンアミドアニオン構造又は環に結合するスルホンイミドアニオン構造を有する有機アニオン、及び
(B)カウンターカチオン
を有する塩化合物を含有する、硬化性組成物。 - 前記カウンターカチオンが、ジアリールヨードニウムカチオン、又はトリアリールスルホニウムカチオンである、請求項1~9のいずれか1項に記載の硬化性組成物。
- 前記カウンターカチオンがシアニン系色素におけるカウンターカチオンである、請求項1~9のいずれか1項に記載の硬化性組成物。
- 前記カウンターカチオンが、アルカリ金属イオン、アルカリ土類金属イオン、又は窒素原子上に正電荷が存在する有機カチオンである、請求項1~9のいずれか1項に記載の硬化性組成物。
- 赤外線吸収剤を更に含む、請求項1~10、及び12のいずれか1項に記載の硬化性組成物。
- 前記赤外線吸収剤が、シアニン系色素である、請求項13に記載の硬化性組成物。
- 重合性化合物を更に含む、請求項1~14のいずれか1項に記載の硬化性組成物。
- 酸発色剤を更に含む、請求項1~15のいずれか1項に記載の硬化性組成物。
- ポリマー粒子を更に含む、請求項1~16のいずれか1項に記載の硬化性組成物。
- バインダーポリマーを更に含む、請求項1~17のいずれか1項に記載の硬化性組成物。
- 請求項1~18のいずれか1項に記載の平版印刷版用硬化性組成物。
- 請求項1~19のいずれか1項に記載の硬化性組成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。
- 前記画像記録層上に、保護層を有する、請求項20に記載の平版印刷版原版。
- 請求項20又は21に記載の平版印刷版原版を画像露光する工程と、
印刷機上で印刷インキ及び湿し水よりなる群から選ばれた少なくとも1つにより、前記画像記録層の未露光部分を除去する工程と、を含む平版印刷版の作製方法。 - 請求項20又は21に記載の平版印刷版原版を画像露光する工程と、
pHが2~11の現像液により前記画像記録層の未露光部分を除去する工程と、を含む平版印刷版の作製方法。
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Cited By (11)
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WO2020262695A1 (ja) * | 2019-06-28 | 2020-12-30 | 富士フイルム株式会社 | 機上現像型平版印刷版原版、平版印刷版の作製方法、及び、平版印刷方法 |
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