WO2023071053A1 - 一种用于光敏阴图型平版印刷版的可成像组合物及其制版方法 - Google Patents

一种用于光敏阴图型平版印刷版的可成像组合物及其制版方法 Download PDF

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Publication number
WO2023071053A1
WO2023071053A1 PCT/CN2022/084721 CN2022084721W WO2023071053A1 WO 2023071053 A1 WO2023071053 A1 WO 2023071053A1 CN 2022084721 W CN2022084721 W CN 2022084721W WO 2023071053 A1 WO2023071053 A1 WO 2023071053A1
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Prior art keywords
printing plate
lithographic printing
development
imageable composition
imageable
Prior art date
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Ceased
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PCT/CN2022/084721
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English (en)
French (fr)
Inventor
翁银巧
应作挺
高邈
徐能平
马显瑶
潘枫
常士旺
金剑臣
陶烃
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ZHEJIANG KONITA NEW MATERIALS CO Ltd
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ZHEJIANG KONITA NEW MATERIALS CO Ltd
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Priority to KR1020247015639A priority Critical patent/KR20240089598A/ko
Priority to EP22884969.1A priority patent/EP4406741A4/en
Priority to US18/704,448 priority patent/US20250036026A1/en
Publication of WO2023071053A1 publication Critical patent/WO2023071053A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
    • B41N3/00—Preparing for use and conserving printing surfaces
    • B41N3/08—Damping; Neutralising or similar differentiation treatments for lithographic printing formes; Gumming or finishing solutions, fountain solutions, correction or deletion fluids, or on-press development
    • 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
    • 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
    • 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
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • 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
    • 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
    • G03F7/322—Aqueous alkaline compositions
    • 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

Definitions

  • the invention belongs to the technical field of preparation of lithographic printing plates, and in particular relates to an imageable composition for photosensitive negative-type lithographic printing plates and a plate-making method thereof.
  • a CTP printing plate precursor called "on-press development” or “process-free” and its plate-making method have been proposed.
  • This lithographic printing plate precursor can The unexposed portions of the image-recording layer are removed by mechanical contact of on-press ink and/or fountain solution by a rotating cylinder to obtain a lithographic printing plate.
  • the treatment-free CTP plate has obvious advantages in energy saving and emission reduction. First of all, the treatment-free CTP plate does not need to use chemical reagents for special treatment, which saves the high cost of washing and saves the cost of purchasing chemical reagents and related instruments. and maintenance costs. Secondly, the treatment-free CTP plate does not need to use chemical medicine to wash the plate, and there is one less processing procedure than the traditional CTP plate, which simplifies the production process, makes the operation easier, and saves production and preparation time.
  • EP 1342568 discloses a method of making thermally sensitive CTP lithographic printing plates, allowing a thermographic precursor comprising hydrophobic thermoplastic polymer particles which coalesce when heated to be developed with a protective colloid.
  • EP 1751625 provides a method for making lithographic plates from photopolymer CTP printing plate precursors, the exposed plate is a simplified process in which developing and gumming occur simultaneously in a single bath with a protective gum. Since the unexposed areas on the photopolymer printing plate are removed by the gumming step, the exposed plate can be stored in ambient light for a long time before it is installed on the printing press, and before the printing plate is installed on the printing press Can provide visible images. In addition, treatment with protective glue provides better removal than on-press treatment with fountain solution and ink.
  • thermosensitive and photosensitive After decades of development in the field of CTP lithographic printing plates, two mainstream trends have been formed: thermosensitive and photosensitive.
  • Thermal technology uses near-infrared (wavelength 830nm) laser imaging, while photosensitive technology uses ultraviolet and visible light (wavelength 380- 405nm) laser imaging.
  • Chinese patent document CN106313870B discloses a method for preparing a heat-sensitive negative-working CTP lithographic printing plate. This patent document adopts the method of directly developing and imaging on a printing machine after exposure, or first going through low-chemical development and imaging after exposure, and then applying to a printing press to achieve instant The plate-making method of off-machine development and on-machine development can be realized at the same time, satisfying customers to choose a more practical method according to the actual situation.
  • the ultraviolet light negative-working CTP lithographic printing plate requires less energy for exposure, and the design needs to improve the light for the imageable composition to change from hydrophilic to lipophilic. sensitivity.
  • the present invention adopts polyfunctional urethanized acrylate or polyfunctional urethanized methacrylate containing high crosslink density, through diisocyanate, polyol, hydroxyethyl (meth)acrylate, etc. Condensation reaction of components to prepare free radical polymerizable compounds; use photoinitiators that can quickly produce free radical crosslinking under ultraviolet light radiation and development accelerators with high tolerance to improve photosensitivity and imaging functions; thus achieving A breakthrough in process-free CTP lithographic printing plate technology.
  • the technical problem to be solved by the present invention is to overcome the large amount of corrosive developer produced in the plate-making process of photosensitive CTP lithographic printing plates, and solve the single defect of the actual developing process, thereby providing a kind of "off-machine developing” and can be used.
  • the flexible development process of "on-machine development” realizes the imageable composition that meets the actual needs of customers and the photosensitive negative-type lithographic printing plate made from the imageable composition.
  • An imageable composition provided by the present invention comprises the following components in parts by mass:
  • the free radical polymerizable compound is a polymerizable monomer and/or oligomer containing at least one ethylenically unsaturated double bond;
  • the photoinitiator has one or more absorption peaks or absorption shoulders in the UV-violet range;
  • the binder is a carbon-containing polymer in the main chain
  • the development accelerator is a low molecular weight hydrophilic organic compound or a high molecular weight hydrophilic polymer.
  • the photoinitiator is sensitive to radiation in the wavelength range of 350nm-450nm.
  • the polymerized monomer and/or oligomer is acrylate, methacrylate, urethane acrylate, urethane methacrylate, epoxy acrylate or epoxy methacrylate, poly One or more of alcohol acrylates, polyol methacrylates, urethane acrylates, urethane methacrylates, polyether acrylates, and polyether methacrylates.
  • the photoinitiator is one of onium salt, trihalomethyl compound, carbonyl compound, azide compound, coumarin, ketocoumarin, anthraquinone, organoboron compound, oxime ester or phosphine oxide one or more species.
  • the carbon-containing polymer in the main chain is acrylic acid, methacrylic acid, acrylate, methacrylate, acrylamide, methacrylamide, styrene and styrene derivatives, acrylonitrile, methacrylonitrile A polymer derived from at least one of N-substituted cyclic imides and maleic anhydride as repeating units.
  • the average molecular weight of the carbon-containing polymer in the main chain is 5,000-100,000.
  • the low-molecular-weight hydrophilic organic compound used as a developing accelerator is polyhydric alcohol and their ether or ester derivatives, organic amine and their salt, organic sulfonic acid and their salt;
  • the high molecular weight hydrophilic polymers of the accelerator are polyethylene glycol, gum arabic, starch, cellulose, dextrin, polysaccharide, and those containing carboxyl, sulfonic acid, phosphonic acid, amide, vinylpyrrolidone One or more of homopolymers or copolymers.
  • the present invention also provides a plate-making method of a photosensitive negative-working lithographic printing plate, which is characterized in that: comprising the following steps:
  • the developing process is any one of the following: (i) On-machine development: Development is performed on-press using fountain solutions and/or lithographic inks; (ii) off-press development: development is performed in a processor off-press using a developer solution.
  • the imageable coating in the plate-making method includes the following components in parts by mass:
  • the free radical polymerizable compound is a polymerizable monomer and/or oligomer containing at least one ethylenically unsaturated double bond;
  • the photoinitiator has one or more absorption peaks or absorption shoulders in the UV-violet range;
  • the binder is a carbon-containing polymer in the main chain
  • the development accelerator is a low molecular weight hydrophilic organic compound or a high molecular weight hydrophilic polymer.
  • the developing solution used for off-machine development in the plate-making method contains carbonate and/or bicarbonate, and the mass fraction of carbonate and/or bicarbonate in the developing solution is 1-20%,
  • the developer has a pH of 6-11.
  • the carbonate in the developing solution is an alkali metal carbonate
  • the bicarbonate in the developing solution is an alkali metal bicarbonate
  • alkali metal carbonate is at least one of sodium carbonate, potassium carbonate or lithium carbonate
  • the alkali metal bicarbonate is at least one of sodium bicarbonate, potassium bicarbonate or lithium bicarbonate.
  • the developing solution further includes at least one of surfactant and/or water-soluble polymer compound.
  • the mass concentration of the surfactant in the developing solution is 0.1-10%
  • the mass concentration of the water-soluble polymer compound in the developing solution is 0.1-20%;
  • the pH value of the developer is preferably 7-10.
  • the substrate with a hydrophilic surface or endowed with a hydrophilic layer is preferably an aluminum substrate that has been electrolytically roughened and anodized.
  • step (3) before the developing process, a step of preheating the exposed printing plate precursor is also included.
  • the imageable coating may comprise one or more layers.
  • the present invention also provides a photosensitive negative-working lithographic printing plate produced by the above-mentioned plate-making method.
  • a poly Functional urethanized (meth)acrylates, photoinitiators that can quickly produce free radical crosslinking under ultraviolet light radiation and high-tolerance development accelerators are selected to increase the speed of exposure light and imaging functions, and realize
  • a poly Functional urethanized (meth)acrylates, photoinitiators that can quickly produce free radical crosslinking under ultraviolet light radiation and high-tolerance development accelerators are selected to increase the speed of exposure light and imaging functions, and realize
  • it can effectively adapt to a variety of development processes, thereby ensuring that customers can flexibly choose development processes according to actual needs, such as "off-machine development” and "on-machine development”, and choose Different development processes will not damage the final development effect.
  • the developer selected in the off-machine development process mainly contains carbonate and bicarbonate, does not contain highly corrosive alkaline substances, and reduces waste. discharge of liquid; and carbonate ions and bicarbonate ions, exhibit a buffer effect and can prevent fluctuations in pH even when the developer is used for a long time. Therefore, deterioration of developing performance caused by fluctuations in pH, occurrence of development scum, and the like are suppressed.
  • off-press development in the present invention refers to the step of removing the image-recording layer of a lithographic printing plate precursor by contact with a liquid (usually a developer solution) in a device (usually an automatic plate processor), The surface of the hydrophilic substrate is thus exposed;
  • on-press development refers to the step of removing the image-recording layer of a lithographic printing plate precursor by contact with ink and/or fountain solution on-press, thereby exposing The surface of a hydrophilic substrate;
  • treatment-free refers to a process of platemaking that does not require any mechanical or chemical treatment after exposure and prior to printing, unless otherwise specified.
  • the plate-making method of the lithographic printing plate of the present invention comprises: with or without a preheating step, the said exposed printing plate precursor is removed through a developing process to remove the said unexposed area, said developing process is as follows Any one of: (i) on-machine development: use fountain solution and/or lithographic printing ink to carry out the development process on the printing press; (ii) off-machine development: use neutral or weakly alkaline developer to print The developing process is carried out in a plate processor outside the machine, and the developing solution includes carbonate and/or bicarbonate.
  • the printing plate precursors of the present invention are "on-press developable", i.e., the printing plate precursors are mounted directly on the printing press and the plate cylinders are rotated while fountain solution and/or ink are supplied to the printing plate precursors on the imageable coating.
  • the non-exposed areas of the imageable coating are removed from the support after a number of revolutions of the plate cylinder, preferably less than 50 revolutions, by passing a suitable fountain solution, lithographic ink, or a combination of both during printing in any order Unexposed areas of the imageable coating are removed.
  • only the fountain solution is supplied to the printing plate when the printing press is first started, and then after a few revolutions of the apparatus, the ink is supplied.
  • the supply of fountain solution and ink can be started at the same time when the printing press is first started, or only the ink can be supplied to the printing plate at the beginning, and then after a few revolutions of the equipment, it can be started. Start supplying fountain solution.
  • a single fluid ink may be supplied to the plate for on-press processing.
  • Single-fluid inks consist of an ink phase (also known as a hydrophobic or lipophilic phase) and a polar phase, which replaces the aqueous fountain solution used in conventional offset printing. Examples of suitable single fluid inks are described in US Patent 4,045,232; US Patent 4,981,517 and US Patent 6,140,392.
  • the single fluid ink comprises an ink phase and a polyol phase as described in WO 00/32705.
  • This type of development process avoids the use of traditional alkaline developers and the use of separate development equipment.
  • the off-machine developing process of the present invention is not particularly limited, and it may be developed by a known method. Development can be accomplished using so-called “manual" development, “dip” development, or processing with automatic development equipment, usually a processor. In the case of “manual” development, development is performed by abrading the entire imaged element with a sponge or cotton pad thoroughly soaked with a suitable developer (described below), followed by rinsing with water. "Dip" development involves immersing the imaged element in an agitated tank or pan containing a suitable developer for 10-60 seconds (especially 20-40 seconds), followed by rinsing with water, with or without a sponge or Cotton pad sanding.
  • the application of automatic developing equipment is well known and generally involves pumping developer into a developing tank and spraying it from spray nozzles.
  • the imaged element is contacted with the developer in a suitable manner.
  • the apparatus may also include suitable sanding means such as brushes or rollers and a suitable number of delivery rollers.
  • Some developing equipment includes a laser exposure device and the equipment is divided into an imaging section and a developing section.
  • the processing solution or developer
  • the imaging element can be brushed with the rinse solution, or it can be poured onto the imaging surface or spray nozzle systems such as those described in EP 1,788,431 and U.S. Patent 6,992,688 (Shimazu et al.)
  • the imaged surface is developed by spraying with force sufficient to remove the unexposed areas.
  • the imaged element can be dipped in a processing solution and abraded manually or with equipment.
  • Suitable off-press development equipment has at least one roller for sanding or brushing the imaged element while applying the developer solution.
  • a processing device By using such a processing device, it is possible to more completely and rapidly remove the unexposed areas of the imaging layer of the printing plate. Residual developer can be removed (e.g., using a squeegee or roller) or left on the resulting printing plate without any rinsing steps. Excess developer can be collected in the tank and used several times, replenished if necessary from the reservoir.
  • the developer replenisher can be of the same concentration as the developer used in processing, or it can be provided in concentrated form and diluted with water at an appropriate time.
  • the developing process may always use fresh liquid, but it is preferable to circulate the developing liquid after the developing process through a filter so as to be reused.
  • a filter for filtering the developing solution used in the above-mentioned developing step, any filter can be used as long as it can filter foreign matter mixed in the developing solution.
  • polyester resin, polypropylene resin, polyethylene resin, cellulose resin, cotton, and the like are preferably used as the material of the filter.
  • the mesh diameter of the filter is preferably 5 to 500 ⁇ m, more preferably 10 to 200 ⁇ m, and even more preferably 20 to 100 ⁇ m.
  • the off-machine developing step of the present invention is preferably carried out by an automatic processor equipped with a rubbing member, wherein the image-exposed lithographic printing plate precursor is rubbed while being transported;
  • an automatic processor equipped with a rubbing member, wherein the image-exposed lithographic printing plate precursor is rubbed while being transported;
  • U.S. Patent Nos. 5,148,746 and 5,568, 768 and British Patent 2,297,719 are particularly preferred automatic processors that use a rotating brush roller as the friction member.
  • the rotary brush roller a known rotary brush roller manufactured by inserting a brush material in a plastic or metal roller can be used.
  • plastic fibers e.g. polyester-based, e.g. polyethylene terephthalate or polybutylene terephthalate, polyamide-based, e.g.
  • nylon 6.6 or nylon 6.10) can be used.
  • polyacrylic bases such as polyacrylonitrile or polyalkyl(meth)acrylates
  • polyolefinic bases such as polypropylene or polystyrene
  • a brush material having a fiber bristle diameter of 20 to 400 ⁇ m and a bristle length of 5 to 30 mm can be preferably used.
  • the outer diameter of the rotating brush roller is preferably 30 to 200 mm, and the peripheral speed of the brush on the rubbing plate is preferably 0.1 to 5 m/sec.
  • the direction of rotation of the rotating brush rollers may be the same direction or the opposite direction with respect to the conveying direction of the lithographic printing plate precursor, but when two or more rotating brush rollers are used, it is preferable that at least one of them rotates relative to the conveying direction.
  • the brushrolls rotate in the same direction, while at least one rotating brushroll rotates in the opposite direction. With such a configuration, the non-image area of the photosensitive layer is more stably removed.
  • the plate-making method of the planographic printing plate of the present invention can adopt conventional three-bath development system
  • the three-bath development system is a method for sequentially performing the three processing steps of the off-machine developing step, the water washing step, and the gluing step, and the processing solutions in the respective baths are used to carry out the respective processing steps, that is, the developing process with at least three processing baths. system.
  • the water washing step and the gumming step are not performed before and after the above-mentioned off-machine developing step, and only the developing step using the above-mentioned developing solution is used as a processing step, that is, a single processing bath is required. (also known as single-bath processing).
  • the resulting lithographic printing plate can be placed on a cylinder of a printing press and printed by applying ink and fountain solution to the printing side of the imaged and developed element.
  • the developing solution used in the plate-making method of the lithographic printing plate of the present invention is a neutral or slightly alkaline aqueous solution or aqueous dispersion containing at least carbonate, bicarbonate or a combination of both.
  • a buffer effect is exhibited and fluctuations in pH can be prevented even when the developer is used for a long time. Therefore, deterioration of developing performance caused by fluctuations in pH, occurrence of development scum, and the like are suppressed.
  • the present invention preferably uses a combination of carbonate and bicarbonate, or carbonic acid can be generated by adding carbonate to the developer and subsequently adjusting the pH ions and bicarbonate ions.
  • the carbonate or bicarbonate used is not particularly limited, and alkali metal salts thereof are preferred.
  • alkali metal salts lithium carbonate, lithium bicarbonate, sodium carbonate, sodium bicarbonate, potassium carbonate, and potassium bicarbonate are exemplified; sodium carbonate, sodium bicarbonate, potassium carbonate, and potassium bicarbonate are preferred, and sodium carbonate and sodium hydrogen.
  • the alkali metal salts may be used alone or in combination of two or more thereof.
  • the total amount of carbonate and bicarbonate is preferably 1 to 20% by weight, more preferably 3 to 15% by weight, based on the weight of the developing aqueous solution.
  • the developer solution of the present invention may also contain a surfactant (eg, anionic, nonionic, cationic or amphoteric surfactant).
  • a surfactant eg, anionic, nonionic, cationic or amphoteric surfactant.
  • anionic surfactants include ricinoleate (aliphates), rosin esters, hydroxyalkane sulfonates, alkane sulfonates, dialkyl sulfosuccinates, linear alkylbenzene sulfonates, branched Salts of alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkylphenoxypolyoxyethylene propylsulfonates, polyoxyethylene alkylsulfophenyl ethers, N-methyl-N-oil Sodium Taurate, Disodium Monoamide N-Alkyl Sulfosuccinate, Petroleum Sulfonate, Sulfated Castor Oil, Sulfated Tallow, Sulfate Salts of Aliphatic Alkyl Esters, Salts of Alkyl Sulfates , sulfate esters of polyoxyethylene alkyl ethers, sulfate ester salts of alipha
  • anionic surfactants include sodium salts of alkylated naphthalenesulfonates, disodium methylene-binaphthalene-disulfonates, sodium alkylbenzenesulfonates, alkylphenoxybenzenedisulfonates sodium sulfonate, sulfonated alkyl-diphenyl ether, ammonium or potassium perfluoroalkyl sulfonate and sodium dioctyl-sulfosuccinate.
  • nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, where the aryl group can be phenyl, naphthyl or aromatic heterocyclic groups, polyoxyethylene polystyrene Phenyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene polyoxypropylene block polymer, partial ester of glycerol fatty acid, partial ester of sorbitan fatty acid, partial ester of pentaerythritol fatty acid Esters, Propylene glycol mono fatty acid esters, Partial esters of sucrose fatty acids, Partial esters of polyoxyethylene sorbitan fatty acids, Partial esters of polyoxyethylene sorbitan fatty acids, Polyethylene glycol fatty esters, Partial esters of polyglycerol fatty acids, polyoxyethylated castor oil, partial esters of polyoxyethylene glycerol fatty acids, fatty diethanolamide
  • nonionic surfactants include ethylene oxide adducts of sorbitol and/or sorbitan fatty acid esters, polypropylene glycol ethylene oxide adducts, dimethylsiloxane-ethylene oxide alkane block copolymers, dimethylsiloxane-(propylene oxide-ethylene oxide) block copolymers, and fatty acid esters of polyols.
  • the cationic surfactant is not particularly limited, and conventionally known cationic surfactants can be used.
  • alkylamine salts quaternary ammonium salts, polyoxyethylene alkylamine salts and polyethylene polyamine derivatives.
  • amphoteric surfactant usable in the present invention is not particularly limited, and conventionally known amphoteric surfactants can be used. Examples thereof include amino acid-based, betaine-based, and amine oxide-based amphoteric surfactants.
  • ethylene oxide adducts of acetylenic diols or acetylenic alcohols, or fluorine-based, silicon-based, and other surfactants can also be used.
  • Two or more of the above surfactants may be used in combination.
  • a combination of two or more different anionic surfactants or a combination of anionic surfactants and nonionic surfactants may be preferred.
  • the amount of such a surfactant is not particularly limited, but is preferably 0.1 to 10% by weight, more preferably 0.1 to 5% by weight.
  • the developer solution of the present invention may also contain a water-soluble polymer compound, exemplified by soybean polysaccharide, modified starch, gum arabic, dextrin, cellulose derivatives (for example, carboxymethyl cellulose, carboxyethyl cellulose or methyl Cellulose) and its modified products, pullulan, polyvinyl alcohol and its derivatives, polyvinylpyrrolidone, polyacrylamide, acrylamide copolymer, vinyl methyl ether/maleic anhydride copolymer, vinyl acetate /maleic anhydride copolymer, styrene/maleic anhydride copolymer, etc.
  • a water-soluble polymer compound exemplified by soybean polysaccharide, modified starch, gum arabic, dextrin, cellulose derivatives (for example, carboxymethyl cellulose, carboxyethyl cellulose or methyl Cellulose) and its modified products, pullulan, polyvinyl alcohol and its derivatives, polyvinyl
  • soybean polysaccharide modified starch, gum arabic, dextrin, carboxymethylcellulose, polyvinyl alcohol and the like are particularly preferable.
  • the water-soluble polymer compounds may be used in combination of two or more.
  • the content of the water-soluble polymer compound in the developer is preferably 0.1 to 20% by weight, more preferably 0.5 to 10% by weight.
  • the developer in the present invention may contain defoamers, organic acids, inorganic acids, inorganic salts and the like in addition to the above-mentioned components.
  • the antifoaming agent it is preferable to use a conventional silicone-based self-emulsifying type or emulsifying type antifoaming agent, and it is preferable to use a silicone antifoaming agent. Any of emulsification dispersion type, dissolution type, etc. may be used.
  • the content of the antifoaming agent is preferably 0.001 to 1.0% by weight.
  • organic acid ethylenediaminetetraacetic acid, citric acid, acetic acid, oxalic acid, malonic acid, salicylic acid, octanoic acid, tartaric acid, malic acid, lactic acid, levulinic acid, p-toluenesulfonic acid, xylenesulfonic acid, Phytic acid, organic phosphonic acid, etc.
  • Organic acids can also be used in the form of alkali metal or ammonium salts, such as disodium ethylenediaminetetraacetic acid.
  • the content of the organic acid is preferably 0.1 to 5% by weight.
  • the inorganic acid or inorganic salt there are exemplified phosphoric acid, metaphosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, sodium tripolyphosphate, pyrophosphate Potassium phosphate, sodium hexametaphosphate, magnesium nitrate, sodium nitrate, potassium nitrate, ammonium nitrate, sodium sulfate, potassium sulfate, ammonium sulfate, sodium sulfite, ammonium sulfite, sodium bisulfate, nickel sulfate, etc.
  • the content of the inorganic salt is preferably 0.1 to 5% by weight.
  • the pH of the developer in the present invention is not particularly limited as long as it is a pH exhibiting a buffering effect, and is preferably in the range of 6 to 11. And it is particularly preferably in the range of 7 to 10.
  • the lithographic printing plate precursor used in the present invention is characterized in that it has a negative-type image forming ability, that is, the region after the image exposure is cured to form an image part, and the unexposed part is removed by the development treatment as described above, Thus, a non-image portion is formed.
  • the substrate used in the lithographic printing plate precursor of the present invention is not particularly limited. It is sufficient that the substrate has a hydrophilic surface, or at least a surface that is more hydrophilic than the imageable layer.
  • the substrate can be composed of any material commonly used in the preparation of imageable elements such as lithographic printing plates. It is usually in the form of a sheet, film or foil (or web), and has a certain strength stability and ductility, and can resist dimensional changes under the conditions of use to ensure correct color matching during printing.
  • the substrate can be any self-supporting material, including polymer films (such as polyester, polyethylene, polycarbonate, cellulose ester polymers, and polystyrene films), glass, ceramics, metal sheets or foils, or rigid paper (including resin or metal coated paper) or laminates of any of these materials (such as aluminum foil laminated to mylar).
  • polymer films such as polyester, polyethylene, polycarbonate, cellulose ester polymers, and polystyrene films
  • glass such as polyester, polyethylene, polycarbonate, cellulose ester polymers, and polystyrene films
  • ceramics such as polyester, polyethylene, polycarbonate, cellulose ester polymers, and polystyrene films
  • metal sheets or foils such as polystyrene films
  • rigid paper including resin or metal coated paper
  • laminates of any of these materials such as aluminum foil laminated to mylar.
  • Metallic supports include sheets or foils of aluminum, copper, zinc, titanium and alloys thereof.
  • the particularly preferred substrate of the present invention is formed using an aluminum support known in the art, and its preparation method includes grinding and roughening by physical (mechanical) grinding, electrochemical grinding or chemical grinding, followed by acidic grinding. Anodized for treatment.
  • a useful hydrophilic lithographic substrate is an aluminum support that is electrochemically grained and anodized with sulfuric or phosphoric acid.
  • Sulfuric acid anodization of aluminum supports typically produces 1.5-5 g/m 2 , more usually 2.5-4 g/m 2 oxide (coverage) on the aluminum surface.
  • Phosphoric acid anodizing typically produces 1-5 g/m 2 , more typically 1.5-3 g/m 2 oxide on the aluminum surface.
  • higher oxide weights at least 3 g/m 2 ) can provide longer print life.
  • Anodized aluminum supports can also be copolymerized with, for example, silicates, dextrins, calcium zirconium fluoride, hexafluorosilicic acid, polyvinylphosphonic acid (PVPA), vinylphosphonic acid copolymers, methacrylic acid or acrylic acid. Materials such as objects are treated to improve hydrophilicity.
  • the thickness of the substrate can vary but should be sufficient to withstand the wear and tear of printing and flexible enough to be rolled. Commonly used thicknesses are 0.1 mm up to and including 0.7 mm treated aluminum foil.
  • the base substrate can also be a cylindrical surface having an imageable layer thereon, such as part of a printing press.
  • an imaging cylinder has been described in US Patent 5,713,287 (Gelbart).
  • the imageable coatings of the present invention comprise at least an imageable composition of a free radical polymerizable compound, a photoinitiator, a binder, and a development accelerator.
  • "coating an imageable composition on the base” means that the coating of the radiation-sensitive composition can be placed on the base in a direct contact manner, or the coating of the radiation-sensitive composition can be placed on the base and the radiation-sensitive coating. Arranging further layers between layers or on top of the radiation-sensitive coating does not negate the presence of any layers, such as protective layers, undercoats, intermediate layers, backcoats, etc., which are arranged as desired in the lithographic printing plate precursor.
  • Free radically polymerizable compounds are well known to those skilled in the art and have been described in considerable literature, including: "Photoreactive Polymers: The Science and Technology of Resists", A. Reiser, Wiley, New York, 1989, 102- 177 pages, B.M. Monroe; “Radiation Curing: Science and Technology”, S.P. Pappas, Ed., Plenum, New York, 1992, 399-440 pages; "Polymer Imaging", A.B. Cohen and P. Walker; “Imaging Processes a Material “, I.M. Sturge et al., Van Nostrand Reinhold, New York, 1989, pp. 226-262. Additionally, useful free radically polymerizable components are also described in European Patent 1,182,033 (Fujimaki et al.).
  • the radically polymerizable compound is a polymerized monomer or oligomer containing at least one ethylenically unsaturated double bond, which may preferably be selected from the group consisting of acrylates of polyols, methacrylates of polyols, urethane acrylates, One or more of urethane methacrylate, epoxy acrylate, epoxy methacrylate, polyurethane acrylate, polyurethane methacrylate, polyether acrylate, polyether methacrylate.
  • Suitable free radically polymerizable monomers may include, for example, polyfunctional acrylate monomers or polyfunctional methacrylate monomers (e.g., ethylene glycol, trimethylolpropane, pentaerythritol, ethoxylated ethylene glycol, Ethoxylated Trimethylolpropane Acrylate, Ethoxylated Trimethylolpropane Methacrylate, Multifunctional Urethane Acrylate, Multifunctional Urethane acrylates, epoxidized acrylates, and epoxidized methacrylates), and oligomeric amine diacrylates.
  • polyfunctional acrylate monomers or polyfunctional methacrylate monomers e.g., ethylene glycol, trimethylolpropane, pentaerythritol, ethoxylated ethylene glycol, Ethoxylated Trimethylolpropane Acrylate, Ethoxylated Trimethylolpropane Methacrylate, Multifunctional Urethane
  • acrylic monomers or methacrylic monomers may also have further double bonds or epoxide groups.
  • the acrylic or methacrylic monomers may also contain acid (eg carboxylic acid) or base (eg amine) functionality.
  • Useful free radical polymerizable compounds include multifunctional urethane acrylates, urethane acrylates, pentaerythritol tetraacrylate, and other polymerizable monomers apparent to those skilled in the art.
  • the free radically polymerizable component is present in the composition in an amount sufficient to render the UV radiation sensitive composition insoluble in the aqueous developer after radiation exposure. This is generally 25-65% by weight, usually 30-60% by weight, based on the dry weight of the radiation-sensitive composition.
  • the free radical photoinitiators used in the present invention exhibit one or more absorption bands in the UV-violet range, and at least one of these bands extends into the visible range of the electromagnetic spectrum shown, or in the visible The range has a shoulder or one or more other minor bands.
  • onium salts, trihalomethyl compounds, carbonyl compounds, azide compounds, coumarins, ketocoumarins, anthraquinones, organoboron compounds, oxime esters or phosphine oxides for example, one or more of onium salts, trihalomethyl compounds, carbonyl compounds, azide compounds, coumarins, ketocoumarins, anthraquinones, organoboron compounds, oxime esters or phosphine oxides.
  • Suitable onium salts include sulfonium salts, oxysulfoxide onium salts, oxonium salts, sulfoxide onium salts, phosphonium salts, diazonium salts, halonium salts such as iodonium salts.
  • diphenyliodonium chloride diphenyliodonium hexafluorophosphate, (4-methylphenyl)[4-(2-methylpropyl)-phenyl]iodonium hexafluorophosphate, hexafluorophosphate Bis(4-tert-butylphenyl)iodonium fluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium octylsulfate, diphenyliodonium octylthiosulfate, diphenyliodonium 2-carboxylate Phenyliodonium, N-methoxy-a-methylpyridinium p-toluenesulfonate, 4-methoxybenzene-diazonium tetrafluoroborate, 2-cyanoethyl-triphenylphosphonium chloride , bis-[4-[4-
  • Photoinitiators also include trichloromethyltriazine-type initiation systems, as described in U.S. Patent 4,997,745; diaryliodonium salts and photosensitizers, as described in U.S. Patent 5,546,258; spectral sensitizers for visible light activation and Trichloromethyltriazines, as described in U.S. Patent No. 5,599,650; 3-ketocoumarins and polycarboxylic acid co-initiators for UV and visible light activation, such as anilino-N,N-diacetic acid and Dicoinitiators, as described in U.S. Patent No.
  • Suitable free radical initiators include, for example, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-2-triazine, 2-(4-methoxy-1-naphthalene base)-4,6-bis(trichloromethyl)-1,3,5-triazine, anilino-N,N-diacetic acid, 2,2-dimethoxy-2-phenylethylphthalein , 2-methyl-l-[4-(methylthio)phenyl-2-morpholinopropan-l-one, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 3-Benzoyl-7-methoxycoumarin, ketone coumarin 93, benzylethanolone or alkyl substituted anthraquinone, tert-butylammonium butyl borate triphenyl and triphenyl (n-butyl ) Tetraethylammonium borate.
  • the initiator composition comprising one or more initiator compounds is present in the radiation-sensitive composition in an amount of 0.5-25%, preferably at least 1% and up to and including 20%, based on the radiation-sensitive composition The total solids of the article or the dry weight of the coated imageable layer.
  • the binder of the present invention is a polymer containing carbon in the main chain, and any one or any of binder polymers known in the art to be used in the photosensitive layer of a negative-working lithographic printing plate precursor can be used without limitation. Two or more.
  • Useful polymeric binders may be homogeneous, i.e. dissolved in the coating solvent, or may be present as discrete particles and include, but are not limited to, acrylic acid, methacrylic acid, acrylate-derived polymers, methacrylate-derived polymers, polyvinyl acetals, phenolic resins, polymers derived from styrene and its derivatives, acrylonitrile, methacrylonitrile, N-substituted cyclic imides or maleic anhydride, such as Those described in European Patent 1,182,033 (noted above) and US Patent 6,309,792 (noted above), US Patent 6,569,603 (noted above) and US Patent 6,893,797 (Munnelly et al.). Also useful are the vinyl carbazole polymers described in US Patent 7,175,949 (Tao et al.).
  • useful polymeric binders are particulate polymers that are distributed (usually uniformly) throughout the imageable layer. These polymers have an average particle size in the range of 10-10,000 nm (usually 20-800 nm) in particle diameter.
  • the polymeric binder is solid at room temperature and is typically a non-elastomeric thermoplastic.
  • the polymeric binder contains both hydrophilic and hydrophobic regions, which are believed to be important for enhancing the difference between exposed and unexposed areas by promoting developability, the presence of the discrete particles tending to promote the unexposed areas. Developing ability. Specific examples of polymeric binders of this embodiment are described in U.S.
  • Patent 6,899,994 (noted above), WO2009/030279 (Andriessen et al.), U.S. Patent 7,261,998 (Hayashi et al.), U.S. Pat. Patent 7,659,046 (Munnelly et al.) and European Patent 1,614,540 (Vermeersch et al.)
  • the imageable layer may optionally contain one or more co-binders.
  • co-binders are, for example, cellulose derivatives, polyvinyl alcohol, polyacrylic acid, polymethacrylic acid, polyvinylpyrrolidone, polylactide, polyvinylphosphonic acid, synthetic copolymers such as alkoxy Polyethylene glycol acrylate copolymer, alkoxy polyethylene glycol methacrylate copolymer.
  • Polymers used as binders typically have an average molecular weight of 2,000-500,000, preferably 5,000-100,000.
  • the total amount of all binder polymers used is usually 10-60% by weight, preferably 20-60% by weight, relative to the total weight of the non-volatile components of the composition.
  • the development accelerator used in the imageable composition of the present invention is a low-molecular-weight hydrophilic organic compound or a high-molecular-weight hydrophilic organic compound. permanent polymer.
  • the low-molecular-weight hydrophilic organic compound used as a development accelerator is one or more of polyols and their ether or ester derivatives, organic amines and their salts, organic sulfonic acids and their salts.
  • examples include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol and tripropylene glycol, glycerin, pentaerythritol and tris(2-hydroxyethyl)isocyanurate, triethanolamine, diethanolamine and Monoethanolamine, toluenesulfonic acid, sodium dodecylbenzenesulfonate, sodium dibutylnaphthalenesulfonate, sodium dioctylsuccinatesulfonate, 10L-45, emulsifier OS, 3B2, ABL.
  • the high-molecular-weight hydrophilic polymer used as a development accelerator is polyethylene glycol, gum arabic, starch, cellulose, dextrin, polysaccharide, and a group containing carboxyl, sulfonic acid, phosphonic acid, amide group , one or more of homopolymers or copolymers of vinylpyrrolidone monomers.
  • the addition amount of the development accelerator is 1-20% by weight, preferably 1-15% by weight relative to the weight of the total solid content of the imageable coating.
  • composition described in the present invention can also include various additives in conventional amounts, such as surfactants, colored dyes, adhesion promoters, contrast dyes, polymerization inhibitors, antioxidants or combinations thereof, Or any other add-on commonly used in lithographic techniques.
  • additives such as surfactants, colored dyes, adhesion promoters, contrast dyes, polymerization inhibitors, antioxidants or combinations thereof, Or any other add-on commonly used in lithographic techniques.
  • the present invention may be formed by suitably applying the imageable composition described above to the substrate described above to form a printing plate precursor having an imageable coating.
  • the imageable composition is dispersed or dissolved in a suitable coating solvent to form a mixed solution, and is coated with suitable equipment and procedures such as spin coating, knife coating, gravure coating, die coating, and slot coating.
  • suitable equipment and procedures such as spin coating, knife coating, gravure coating, die coating, and slot coating.
  • the mixed solution is applied to the surface of the substrate support, also by spraying onto a suitable support such as a printing cylinder of a printing machine
  • the composition is applied, and then dried in an oven at 70° C. to 160° C. to remove the coating solvent to obtain the lithographic printing plate precursor.
  • solvent used herein depends on the nature of the polymeric binder and other non-polymeric components in the composition, typically coating solvents used under conditions and techniques well known in the art, Examples include: acetone, cyclohexanone, methanol, ethanol, propanol, butanol, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, 1-methoxy-2-propanol, 2-ethoxy -Ethanol, 2-methoxyethyl acetate, 1-methoxy-2-propyl acetate, dimethoxyethane, methyl lactate, ethyl lactate, N,N-dimethyl Formamide, N,N-dimethylacetamide, tetramethylurea, N-methylpyrrolidone, dimethylsulfoxide, ⁇ -butyrolactone, etc., but not limited to these solvents.
  • a solvent can be used individually by 1 type or in mixture of 2 or
  • the coat weight of the imageable layer after drying is generally at least 0.1-5 g/m 2 , preferably 0.5-3 g/m 2 .
  • a protective coating comprising one or more surface protective compounds on the imageable coating. layer.
  • any one of water-soluble polymers and water-insoluble polymers can be appropriately selected and used, and two or more kinds can be used in combination as necessary.
  • gum arabic for example, gum arabic, pullulan, cellulose derivatives such as carboxymethylcellulose, carboxyethylcellulose or methylcellulose, dextrin, cyclodextrin, vinyl alcohol, polyvinyl alcohol , Vinylpyrrolidone, polyvinylpyrrolidone, polysaccharides, homopolymers and copolymers of acrylic acid, methacrylic acid or acrylamide, etc.
  • a water-soluble polymer compound with relatively excellent crystallinity.
  • polyvinyl alcohol when polyvinyl alcohol is used as the main component, it can bring the best results for basic properties such as oxygen barrier property and development removability. .
  • the lasers used to expose the lithographic printing plate precursors of the present invention may be carbon arc lamps, high pressure mercury lamps, xenon lamps, metal halide lamps, fluorescent lamps, tungsten lamps, halogen lamps, helium cadmium lamps, Laser, argon ion laser, FD-YAG laser, helium-neon laser, semiconductor laser (350nm-450nm) perform image exposure on the photosensitive layer.
  • the high-performance lasers or laser diodes used in currently commercially available image digital platesetters emit at 405nm, and the imaging device can be configured as a flatbed recorder or a drum recorder, where the imageable element is mounted to the inside or outside of the drum Cylindrical surface.
  • Suitable exposure equipment for example: CTCP/UV imaging machines of CRON (Korei) and AMSKY (Paulite), Xeikon UV device of BasysPrint, Xpose UV machine of Liischer, Nautilius equipment of ECRM.
  • CTCP/UV imaging machines of CRON (Korei) and AMSKY (Paulite)
  • Xeikon UV device of BasysPrint Xpose UV machine of Liischer
  • Nautilius equipment of ECRM Depending on the sensitivity of the radiation-sensitive layer, the imaging is generally performed with an energy of 30 mJ/cm2 to 500 mJ/cm2, preferably 50 mJ/cm2 to 300 mJ/cm2.
  • the printing plate precursor can be treated with or without preheating as desired.
  • the printing plate that has been preheated before development can more or less improve its printing durability.
  • the imaged lithographic printing plate produced by the aforementioned development process is mounted on a printing press, coated with printing ink and a fountain solution for printing, wherein the fountain solution is filled with non-imaged areas (hydrophilic groups revealed by the imaging and processing steps). surface of the substrate) and ink is absorbed by areas of the imaging layer (not removed).
  • the ink is then transferred to a suitable receiving material such as cloth, paper, metal, glass or plastic to provide the desired imprint of the image thereon.
  • a suitable receiving material such as cloth, paper, metal, glass or plastic to provide the desired imprint of the image thereon.
  • an intermediate “transfer roll” can be used to transfer the ink from the imaging member to the receiver material.
  • Binder A is a polymer dispersion of 90% by weight styrene and 10% by weight polyethylene glycol methyl ether methacrylate in propanol/water (80/20 by volume) with a solids content of 23.7% .
  • Binder B is a solution of a polymer containing 80% by weight methyl methacrylate and 20% by weight methacrylic acid in 2-butanone at a concentration of 33%.
  • Binder C is a polymer dispersion containing 92% by weight methyl methacrylate and 8% by weight polyethylene glycol methyl ether methacrylate in propanol/water (80/20 by volume), solids content was 24.0%.
  • Binder D is a polymer containing 20% by weight styrene, 70% by weight cyanoethyl acrylate and 10% by weight polyethylene glycol methyl ether methacrylate in propanol/water (80/20 by volume) Dispersion with a solids content of 23.8%.
  • Binder E is a polymer solution containing 90% by weight of allyl methacrylate and 10% by weight of polyethylene glycol methyl ether methacrylate in 2-butanone, with a solid content of 10%.
  • Free-radically polymerizable compound A reaction product of 1,6-hexamethylene diisocyanate with hydroxyethyl acrylate and pentaerythritol triacrylate (polymer solution in 2-butanone, solids content 80%).
  • Sartomer 355 is a multifunctional acrylic monomer available from Sartomer Co., Inc.
  • PI-18 is 2-(4-methoxy-1-naphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, available from DKSH Group (Zurich, Switzerland) .
  • 250 is (4-methoxyphenyl)[4-(2-methylpropyl)phenyl]iodonium hexafluorophosphate, commercially available from Ciba Specialty Chemicals (Tarrytown, NY).
  • PI-0591 is an iodonium salt initiator, which can be purchased from Tokyo Chemical Industry Co., Ltd., Japan.
  • BYK-341 organic silicon surface additive can be purchased from German BYK company.
  • TMSPMA stands for 3-(methacryloyloxy)-propyltrimethoxysilane.
  • Developer solution A is a solution prepared as follows: in 750 g of deionized water, dissolve successively under stirring: 13 g of sodium carbonate and 7 g of sodium bicarbonate; 50 g of sodium dodecylbenzenesulfonate; 25 g of gum arabic; 50 g of ethylene glycol Monophenyl ether; 20g p-toluenesulfonic acid; 0.1g SE 47 defoamer; deionized water was further added to 1000 g.
  • the pH of developer A was 8.9.
  • Developer solution B is a solution prepared as follows: in 750 g of deionized water, dissolve successively under stirring: 25 g of sodium bicarbonate and 5 g of sodium carbonate; 50 g of sodium n-butylnaphthalene sulfonate; 3.0 g of disodium edetate ;0.1g 47 Defoamer; deionized water was further added to 1000 g.
  • the pH of developer solution B was 7.4.
  • the above-mentioned components are dissolved in a mixed solvent of 20.2g of 1-methoxy-2-propanol, 9.5g of water and 16.5g of 2-butanone, and the solution is covered by the electrochemical coarse Then, it was dried in an oven at 110° C. for 2 minutes to obtain a lithographic printing plate precursor with a coating weight of 1.2 g/m 2 .
  • the lithographic printing plate precursor obtained in this way can use a 405nm laser on the UVP-820G+ CTcP plate-making machine of CRON (Kolei), the drum rotation speed is 500rpm, and the laser power is 45mW.
  • Developer A is rinsed by MASTER VIEW developing machine for 35s to obtain a good image; you can also choose to directly expose the lithographic printing plate precursor through a UV printing machine, and then directly install it on the printing machine to print more than 500 prints with good quality .
  • the above-mentioned components are dissolved in a mixed solvent of 20.2g of 1-methoxy-2-propanol, 9.5g of water and 16.5g of 2-butanone, and the solution is covered by the electrochemical coarse oxidized and anodized aluminum plates, and then dried in an oven at 110°C for 2 minutes to obtain a lithographic printing plate precursor with a coating weight of 1.2 g/m 2 .
  • the lithographic printing plate precursor obtained in this way can use a 405nm laser on the UVP-820G+ CTcP plate-making machine of CRON (Kolei), the drum rotation speed is 500rpm, and the laser power is 45mW.
  • Developer A is rinsed by MASTER VIEW developing machine for 35s to obtain a good image; you can also choose to directly expose the lithographic printing plate precursor through a UV printing machine, and then directly install it on the printing machine to print more than 500 prints with good quality .
  • the above-mentioned components were dissolved in a mixed solvent of 20.2g of 1-methoxy-2-propanol, 9.5g of water and 16.5g of 2-butanone, and the solution was covered by electrochemical roughening by using a spin coating method. oxidized and anodized aluminum plates, and then dried in an oven at 110° C. for 2 minutes, and the weight of the first coating obtained was 1.2 g/m 2 . Then cover the top of the first layer with a solution of gum arabic (3.0g) and water (94.0g), and then dry it in an oven at 110°C for 2 minutes to prepare a lithographic plate with a total weight of double coating of about 2.2g/ m2 Printing plate precursors.
  • the lithographic printing plate precursor obtained in this way can use a 405nm laser on the UVP-820G+ CTcP plate-making machine of CRON (Kolei), the drum rotation speed is 500rpm, and the laser power is 45mW.
  • Developer B is rinsed by MASTER VIEW developing machine for 35s to obtain a good image; you can also choose to directly expose the lithographic printing plate precursor through a UV printing machine, and then directly install it on the printing machine to print more than 500 prints with good quality .
  • the above-mentioned components were dissolved in a mixed solvent of 20.2g of 1-methoxy-2-propanol, 9.5g of water and 16.5g of 2-butanone, and the solution was covered by electrochemical roughening by using a spin coating method. Then, it was dried in an oven at 110° C. for 2 minutes to obtain a lithographic printing plate precursor with a coating weight of 1.2 g/m 2 .
  • the lithographic printing plate precursor obtained in this way can use a 405nm laser on the UVP-820G+ CTcP plate-making machine of CRON (Kolei), the drum rotation speed is 500rpm, and the laser power is 45mW.
  • Developer B is rinsed by MASTER VIEW developing machine for 35s to obtain a good image; you can also choose to directly expose the lithographic printing plate precursor through a UV printing machine, and then directly install it on the printing machine to print more than 500 prints with good quality .
  • the above-mentioned components were dissolved in a mixed solvent of 20.2g of 1-methoxy-2-propanol, 9.5g of water and 16.5g of 2-butanone, and the solution was covered by electrochemical coarse oxidized and anodized aluminum plates, and then dried in an oven at 110° C. for 2 minutes, and the weight of the first coating obtained was 1.2 g/m 2 . Then cover the top of the first layer with a solution of polyvinyl alcohol (3.0g) and water (94.0g), and then dry it in an oven at 110°C for 2 minutes to prepare a double coating with a total weight of about 2.1g/m 2 Lithographic printing plate precursors.
  • the lithographic printing plate precursor obtained in this way can use a 405nm laser on the UVP-820G+ CTcP plate-making machine of CRON (Kolei), the drum rotation speed is 500rpm, and the laser power is 45mW.
  • Developer A is rinsed by MASTER VIEW developing machine for 35s to obtain a good image; you can also choose to directly expose the lithographic printing plate precursor through a UV printing machine, and then directly install it on the printing machine to print more than 500 prints with good quality .

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Abstract

提供了一种用于光敏阴图型平版印刷版的可成像组合物及其制版方法。其中，可成像组合物包括如下质量份数的组分：自由基可聚合化合物25‑65份，光引发剂0.5‑25份，粘结剂10‑60份，显影促进剂1‑20份；制版方法包括如下步骤：（1）在具有亲水表面或亲水层的底基上涂覆可成像组合物得到一种光敏阴图型平版印刷版前体；（2）利用激光按所需图像曝光平版印刷版前体，从而形成曝光区域和未曝光区域；（3）将已曝光的印刷版前体通过显影工序除去未曝光区域制得所需的平版印刷版。采用这种可成像组合物和制版方法能实现"在机显影"或"离机显影"的灵活显影工序、且制得的印刷版具有优异的印刷性能。

Description

一种用于光敏阴图型平版印刷版的可成像组合物及其制版方法 技术领域
本发明属于平版印刷版制备技术领域，具体涉及一种用于光敏阴图型平版印刷版的可成像组合物及其制版方法。
背景技术
平版印刷版领域的最新发展得益于计算机以电子方式对图像信息进行处理、储存、输出的数字化技术得到了越来越广泛的普及，这样的数字化技术所对应的各种新的图像输出方式已付诸实用。由此诞生了数字化的图像信息可以负载于诸如激光这种高会聚性的放射线，并利用该激光对平版印刷版原版直接进行扫描曝光的计算机直接制版(CTP)技术。这类技术由于不再借助传统的胶片膜来制造平版印刷版的优势而备受瞩目，成为平版印刷版领域重要的技术课题之一。
在传统的平版印刷版的制作工序中，需要在曝光后通过显影液溶解去除不需要的感光涂层的处理步骤，这造成了相对费时和增加成本。尤其是近年来，出于对环境保护的考虑，伴随强碱性溶液的显影处理而排出的废液的处置已成为整个产业界非常关注的课题。因此，作为追求进一步简化制版过程和减少处理废水的问题，各种各样的新技术，包括曝光后无需化学显影即可上机的印版前体或是能够以接近中性的水溶液进行离机显影的制作工序，已经成为当今本领域技术研究的挑战课题。
作为满足以上所述的挑战性的制版技术之一，一种被称为“在机显影”或“免处理”的CTP印版前体及其制版方法已经提出，这种平版印刷版前体能够被印刷机上的油墨和/或润版液通过旋转滚筒的机械接触除去图像记录层的未曝光部分，从而得到平版印刷版。免处理CTP版材具有明显的节能减排优势，首先，免处理CTP版材无须使用化学试剂作特别处理，省去了因冲洗而带来的高昂成本，节省了购买化学试剂及相关仪器的成本及维修费用。其次，免处理CTP版材无须使用化学药水冲版，比传统CTP版材少了一道加工工序，简化了生产工艺流程，操作更加简便，节省了生产及准备时间。
用于简化工艺以及解决废液问题的另一方案是采用接近中性的水溶液进行显影，也称为“低化学处理”的制版方法。对比上述的“免处理”技术，该方法好处是在曝光后上印刷机前能够检测图像的质量以及避免印版受环境光的影响造成对未曝光区的沾污。EP 1342568公开了制造热敏CTP平版印刷版的方法，使包含受热时会聚结的疏水热塑性聚合物颗粒的热成像前体可以用保护胶液显影。EP 1751625提供用光聚合物CTP印版前体制造平 印版的方法，曝光版是用保护胶在单一浴槽中显影和上胶同时发生的简化处理过程。由于光聚合物印版上的未曝光区是由上胶步骤除去的，所以在曝光版被安装到印刷机上之前可在环境光中保存很长的时间，以及在印版被安装到印刷机上之前能提供可见图象。此外，用保护胶处理比用润版液和油墨在印刷机上处理有更好的清除作用。
CTP平版印刷版领域经过几十年的发展，已形成了主流趋势热敏和光敏两种，热敏技术采用近红外(波长830nm)的激光成像，而光敏技术则采用紫外和可见光(波长380-405nm)的激光成像。中国专利文献CN106313870B公开了热敏阴图型CTP平版印刷版的制备方法，该专利文献采用曝光后直接上印刷机显影成像，或在曝光后先经由低化学显影成像后再上印刷机，达到即可实现离机显影，同时也可实现在机显影的制版方法，满足客户根据实际情况选择更实用的方法。
目前，国内外免化学处理热敏CTP平版印刷版的市场正在逐年扩大，但是免化学处理光敏平版印刷版仍然局限于紫激光(Violet)领域的低化学处理技术，而光敏免处理平版印刷版在紫外光(UV)领域的开拓还是一片空白。光敏领域上的“在机显影”或“免处理”CTP平版印刷版尚未见市场应用，在实施环保制版以及控制废水排放的发展方面严重落后于热敏CTP平版印刷版技术。因此，研究开发免化学处理光敏CTP平版印刷版是适应绿色印刷和节能环保政策的必然趋势，具有非常积极的意义。
相对于热敏阴图型免处理CTP平版印刷版，紫外光阴图型免处理CTP平版印刷版曝光所需的能量更低，在设计上需要提高可成像组合物从亲水性转变成亲油性的光敏感性。本发明采用含有高交联密度的多官能氨基甲酸酯化的丙烯酸酯或多官能氨基甲酸酯化的甲基丙烯酸酯，通过二异氰酸酯、多元醇、羟乙基(甲基)丙烯酸酯等成份缩合反应制得自由基可聚合化合物；选用在紫外光辐射下能够快速产生自由基交联的光引发剂以及高宽容度的显影促进剂，提高感光速度和成像功能；从而达到在紫外光阴图型免处理CTP平版印刷版技术上的突破。
发明内容
因此，本发明要解决的技术问题在于克服光敏CTP平版印刷版的制版过程中产生大量腐蚀性的显影液，同时解决实显影工序单一的缺陷，从而提供一种既可“离机显影”又可“在机显影”的灵活显影工序，实现满足客户实际需求的可成像组合物以及利用该可成像组合物制成的光敏阴图型平版印刷版。
本发明所提供的一种可成像组合物，包括如下质量份数的组分：
Figure PCTCN2022084721-appb-000001
Figure PCTCN2022084721-appb-000002
其中，所述自由基可聚合化合物为含有至少一个烯类不饱双键的聚合单体和/或寡聚体；
所述光引发剂在UV-紫光范围内具有一个或多个吸收峰或吸收肩带；
所述粘结剂为主链含碳的聚合物；
所述显影促进剂为低分子量亲水性有机化合物或高分子量亲水性聚合物。
优选地，所述光引发剂对波长范围在350nm-450nm的辐射线敏感。
优选地，所述聚合单体和/或寡聚体为丙烯酸酯、甲基丙烯酸酯、氨酯丙烯酸酯、氨酯甲基丙烯酸酯、环氧化物丙烯酸酯或环氧化物甲基丙烯酸酯、多元醇的丙烯酸酯、多元醇的甲基丙烯酸酯、聚氨酯丙烯酸酯、聚氨酯甲基丙烯酸酯、聚醚丙烯酸酯、聚醚甲基丙烯酸酯中的一种或多种。
优选地，所述光引发剂为鎓盐、三卤甲基化合物、羰基化合物、叠氮化合物、香豆素、酮基香豆素、蒽醌、有机硼化合物、肟酯或氧化膦中的一种或多种。
优选地，所述主链含碳的聚合物为丙烯酸、甲基丙烯酸、丙烯酸酯、甲基丙烯酸酯、丙烯酰胺、甲基丙烯酰胺、苯乙烯及苯乙烯衍生物、丙烯腈、甲基丙烯腈、N-取代环状酰亚胺、马来酸酐中的至少一种构成重复单元而衍生出的聚合物。
优选地，所述主链含碳的聚合物的平均分子量为5000-100000。
优选地，所述用作显影促进剂的低分子量亲水性有机化合物为多元醇以及它们的醚或酯衍生物、有机胺以及它们的盐、有机磺酸以及它们的盐；所述用作显影促进剂的高分子量亲水性聚合物为聚乙二醇、阿拉伯树胶，淀粉，纤维素，糊精，多糖，以及含有羧基、磺酸基、膦酸基团、酰胺基团、乙烯基吡咯烷酮单体的均聚物或者共聚物的一种或多种。
本发明还提供了一种光敏阴图型平版印刷版的制版方法，其特征在于：包括如下步骤：
(1)在具有亲水表面或亲水层的底基上涂覆一种可成像组合物得到一种光敏阴图型平版印刷版前体；
(2)图案化曝光所述平版印刷版前体，从而形成曝光区域和未曝光区域；
(3)将已曝光的印刷版前体通过显影工序除去所述未曝光区域获得所需的平版印刷版，其特征在于：所述显影工序为如下的任意一种：(i)在机显影：使用润版溶液和/或平版印刷油墨在印刷机上实施显影；(ii)离机显影：使用一种显影液在印刷机外的冲版机中实施显影。
所述的制版方法中的可成像涂层，包括如下质量份数的组分：
Figure PCTCN2022084721-appb-000003
其中，所述可自由基聚合化合物为含有至少一个烯类不饱双键的聚合单体和/或寡聚体；
所述光引发剂在UV-紫光范围内具有一个或多个吸收峰或吸收肩带；
所述粘结剂为主链含碳的聚合物；
所述显影促进剂为低分子量亲水性有机化合物或高分子量亲水性聚合物。
所述的制版方法中用于离机显影所述的显影液包含碳酸盐和/或碳酸氢盐，所述显影液中碳酸盐和/或碳酸氢盐的质量分数为1-20％，所述显影液的pH值为6–11。
优选地，所述显影液中碳酸盐为碱金属碳酸盐；所述显影液中碳酸氢盐为碱金属碳酸氢盐。
进一步地，所述碱金属碳酸盐为碳酸钠、碳酸钾或碳酸锂中的至少一种；
所述碱金属碳酸氢盐为碳酸氢钠、碳酸氢钾或碳酸氢锂中的至少一种。
进一步地，所述显影液中还包括表面活性剂和/或水溶性高分子化合物中的至少一种。
所述显影液中表面活性剂的质量浓度为0.1-10％；
所述显影液中水溶性高分子化合物的质量浓度为0.1-20％；
所述显影液的pH值优选为7-10。
所述带亲水表面或被赋予亲水层的底基优选为经过电解粗糙化及阳极氧化处理的铝基材。
所述步骤(3)中，所述显影工序之前，还包括对曝光后的所述印刷版前体进行预热处理的步骤。
进一步地，所述可成像涂层可包含一层或多层。
本发明还提供了由上述制版方法制得的光敏阴图型平版印刷版。
与现有技术相比，本发明技术方案具有如下优点：
1)本发明所提供的可成像组合物以及利用该组合物制得的光敏阴图型平版印刷版，通过调控可成像组合物中各组分的种类和含量，采用含有高交联密度的多官能氨基甲酸酯化的(甲基)丙烯酸酯，选用在紫外光辐射下能够快速产生自由基交联的光引发剂以及高宽容度的显 影促进剂，以提升曝光光速度和成像功能，实现了在光敏领域上CTP平版印刷版制版过程中更加环保安全，能有效适应多种显影工序，进而保证客户根据实际需求灵活选择显影工序，如“离机显影”和“在机显影”，而且选择不同的显影工序也不会损害最终的显影效果。
2)本发明所提供的光敏阴图型平版印刷版的制版方法，在离机显影过程中选用的显影液主要含有碳酸盐和碳酸氢盐，不含高腐蚀性的碱性物质，减少废液的排放；而且碳酸根离子和碳酸氢根离子，表现出缓冲剂作用并且即使在长时间使用显影液时可以防止pH的波动。因此，抑制了由pH的波动导致的显影性能的劣化，显影浮渣的出现等。
具体实施方式
为了更好地说明本发明的目的、技术方案和优点，下面将结合具体实施例对本发明做进一步描述。本发明可以以许多不同的形式实施，而不应该被理解为限于在此阐述的实施例。相反，提供这些实施例，使得本公开更为透彻和完整，并且将把本发明的构思充分传达给本领域技术人员，本发明将仅由权利要求来限定。
本发明中术语“离机显影”指的是通过与一种装置(通常是自动冲版机)中的液体(通常是显影剂溶液)接触来除去平版印刷版前体的图像记录层的步骤，由此露出亲水性底基的表面；术语“在机显影”指的是通过与印刷机上的油墨和/或润版液接触的方法除去平版印刷版前体的图像记录层的步骤，从而露出亲水性底基的表面；术语“免处理”是指一种制版方法，它在曝光之后和上印刷机之前不需要任何机械或化学处理，除非另有规定。
以下，对本发明的平版印刷版的制版方法进行详细说明。另外，在说明最具特征性的步骤即显影工序后，再说明其他步骤。
、显影工序：
本发明的平版印刷版的制版方法包括：在有或者没有预热步骤的情况下，将所述已曝光的印刷版前体通过一道显影工序除去所述的未曝光区域，所述显影工序为如下的任意一种：(i)在机显影：使用润版溶液和/或平版印刷油墨在印刷机上进行所述显影工序；(ii)离机显影：使用中性或弱碱性的显影液在印刷机外的冲版机中进行所述显影工序，所述显影液包括碳酸盐和/或碳酸氢盐。
a、在机显影：
本发明的印刷版前体是可“在机显影”的，比如，将印刷版前体直接安装到印刷机上，让印版滚筒旋转，同时将润版液和/或油墨供给到印刷版前体的可成像涂层上。在印版滚筒旋转许多转之后，优选小于50转之后，从载体上除去可成像涂层的非曝光区域，其中在印刷期 间可按任何顺序通过适合的润版溶液、平版油墨或两者的组合除去可成像涂层中的未曝光区域。
在一种优选的实施方案中，在印刷机刚启动时只有润版液供给到印版上，然后在设备转了几转之后，才开始供给油墨。
在另一种可选择的实施方案中，在印刷机刚启动时润版液和油墨的供给可以同时开始，或者在开始时只有油墨供给到印版上，然后在设备转了几转之后，才开始供给润版液。
还有另外一种可选择的实施方案中，可将单流体油墨供给到印版上实现在机处理。单流体油墨的组成为油墨相(也称作疏水或者亲油相)和极性相，该极性相代替了常规胶印中所用的含水润版液。合适的单流体油墨的例子曾在美国专利4，045，232；美国专利4，981，517和美国专利6，140，392描述过。在一种最优选的实施方案中，该单流体油墨包含油墨相和多元醇相，如WO 00/32705所述。
这类显影工序避免使用传统的碱性显影液和使用独立的显影设备。
、离机显影：
本发明的离机显影处理没有特殊限制，利用公知的方法进行显影即可。显影可以使用所谓的“手动”显影、“浸溃”显影或用自动显影设备(通常为冲洗机)的冲洗完成。在“手动”显影的情况下，用充分浸溃有适合的显影剂(如下所述)的海绵或棉垫打磨整个成像元件，接着用水冲洗来进行显影。“浸溃”显影包括将成像元件浸溃在含合适的显影剂的在搅拌下的槽或盘子中保持10-60秒(特别是20-40秒)，接着用水冲洗，可用或者可不用海绵或棉垫打磨。自动显影设备的应用是众所周知的，它一般包括将显影剂泵入显影罐然后从喷雾嘴喷射它。按合适的方式让成像元件与显影剂接触。该设备还可以包括适合的打磨机构(例如刷子或辊子)和适合的数目的输送辊。一些显影设备包括激光曝光装置并且该设备被划分为成像段和显影段。比如，可以采用如下方式将冲洗溶液(或显影剂)施于成像元件上：打磨、喷涂、喷射、浸溃、浸没、窄缝ロ模涂覆(例如参见Maruyama等人的美国专利6，478，483的图I和2)或逆辊涂覆(如Kurui等人的美国专利5，887，214的图4所述)，或用冲洗溶液擦拭外层或让它与含胶料的辊子、浸溃垫或涂覆器接触。例如，可以用冲洗溶液刷涂成像元件，或可以将它倾倒到成像表面上或使用例如在EP 1，788，431和美国专利6，992，688(Shimazu等人)中描述的喷雾嘴系统以足以除去未曝光区域的力通过喷涂成像表面进行显影。同样，可以将成像元件浸于冲洗溶液中并手工或用设备进行打磨。
合适的离机显影设备具有至少一个用于在施加显影液同时打磨或刷涂成像元件的辊子。通过使用此种冲洗装置，可以使印版更完全和迅速地除去成像层的未曝光区域。残留显 影液可以被除去(例如，使用涂刷器或轧辊)或在没有任何冲洗步骤的情况下留在所得的印刷板上。过量显影液可以收集在槽中并使用数次，并如有必要从储器补充。显影补充剂可以具有与冲洗中使用的显影液相同的浓度，或以浓缩形式提供并在合适时间用水稀释。显影过程可以始终使用新鲜的液体，但优选使显影处理后的显影液通过过滤器循环、从而重复使用。用于过滤上述显影工序中使用的显影液的过滤器只要能够将混入显影液中的异物过滤，则可以使用任意过滤器。作为过滤器的材质，优选使用聚酯树脂、聚丙烯树脂、聚乙烯树脂、纤维素树脂、棉等。作为过滤器的网眼孔径，优选为5～500μm、更优选为10～200μm、进一步优选为20～100μm。
本发明的离机显影步骤优选通过配备有摩擦构件的自动处理机进行，其中将图像曝光后的平版印刷版原版在输送的同时进行摩擦处理；如美国专利5，148，746和5，568，768和英国专利2，297，719中所述的自动处理机，特别优选使用旋转毛刷辊作为摩擦构件的自动处理机。对于旋转毛刷辊，可以使用通过在塑料或金属辊中插入毛刷材而制造的已知旋转毛刷辊。作为毛刷的材料，可以使用塑料纤维(例如，聚酯基，例如，聚对苯二甲酸乙二醇酯或聚对苯二甲酸丁二醇酯，聚酰胺基，例如，尼龙6.6或尼龙6.10，聚丙烯酸类基，例如，聚丙烯腈或聚(甲基)丙烯酸烷基酯，和聚烯烃基，例如，聚丙烯或聚苯乙烯)。例如，可以优选使用纤维毛直径为20至400μm且毛长度为5至30mm的刷材。旋转毛刷辊的外径优选为30至200mm，并且在摩擦版面的毛刷的圆周速度优选为0.1至5m/秒。
相对于平版印刷版原版的输送方向，旋转毛刷辊的旋转方向可以是相同方向或相反的方向，但是当使用2根以上旋转毛刷辊时，优选的是，相对于输送方向，至少一个旋转刷辊在相同的方向上旋转，而至少一个旋转刷辊在相反方向上旋转。采用这样的构造，更稳定地除去了光敏层的非图像区。
在本发明的平版印刷版的制版方法中，可采用常规的三浴显影系统，
所述三浴显影系统是依次进行离机显影工序、水洗工序及上胶工序这三个处理工序的方法，各自浴槽中的处理液用来进行各自处理工序、即具有至少3种处理浴槽的显影系统。本发明的平版印刷版的制版方法也可采用在上述离机显影工序的前后不进行水洗工序、上胶工序，仅将利用上述显影液进行的显影工序作为处理工序，即需要利用单个处理浴槽来进行(也称为单浴处理)。
在离机显影冲洗之后，所得的平版印刷板可以放到印刷机的滚筒上，通过将油墨和润版液涂覆到成像并显影的元件的印刷面上进行印刷。
需要说明的是，在本发明中，可以任意在显影工序之后设置干燥工序。特别是，优选设置在自动处理机的最后的工序。
显影液：
本发明的平版印刷版的制版方法中使用的显影液是至少含有碳酸盐、碳酸氢盐或其两者组合的中性或弱碱性的水溶液或水分散液。鉴于存在碳酸根离子和碳酸氢根离子，表现出缓冲剂作用并且即使在长时间使用显影液时可以防止pH的波动。因此，抑制了由pH的波动导致的显影性能的劣化，显影浮渣的出现等。为了使碳酸根离子和碳酸氢根离子同时存在于显影液中，本发明优选使用碳酸盐和碳酸氢盐的组合，或者可以通过将碳酸盐加入到显影液中并且随后调节pH而产生碳酸根离子和碳酸氢根离子。所使用的碳酸盐或碳酸氢盐不受特别限制，优选为其碱金属盐。作为碱金属盐，示例有碳酸锂、碳酸氢锂、碳酸钠、碳酸氢钠、碳酸钾和碳酸氢钾；优选碳酸钠、碳酸氢钠、碳酸钾和碳酸氢钾，且特别优选碳酸钠和碳酸氢钠。碱金属盐可以单独或以其两种以上的组合使用。
基于显影水溶液的重量，碳酸根盐和碳酸氢盐的总量优选为1至20重量％，更优选为3至15重量％。
本发明的显影液还可以含有表面活性剂(例如，阴离子、非离子、阳离子或两性表面活性剂)。
阴离子表面活性剂的例子包括蓖麻油酸酯(aliphates)，松香酸酯，羟基烷烃磺酸酯，烷烃磺酸酯，二烷基磺基琥珀酸酯，直链烷基苯磺酸酯，支化的烷基苯磺酸酯，烷基萘磺酸酯，烷基苯氧基聚氧乙烯丙基磺酸酯，聚氧乙烯烷基磺基苯基醚的盐，N-甲基-N-油基牛磺酸钠，单酰胺N-烷基磺基琥珀酸二钠，石油磺酸酯，硫酸化蓖麻油，硫酸化牛油，脂肪族烷基酯的硫酸酯盐，烷基硫酸酯的盐，聚氧乙烯烷基醚的硫酸酯，脂肪族单甘油酯的硫酸酯盐，聚氧乙烯烷基苯基醚的硫酸酯盐，聚氧乙烯苯乙烯基苯基醚的硫酸酯盐，烷基磷酯的盐，聚氧乙烯烷基醚的磷酯盐，聚氧乙烯烷基苯基醚的磷酯盐，苯乙烯马来酸酐共聚物的部分皂化的化合物，烯烃-马来酸酐共聚物的部分皂化的化合物，和萘磺酸酯福尔马林缩合物。在这些阴离子表面活性剂中，特别优选的是二烷基磺基琥珀酸酯和烷基萘磺酸酯。
合适的阴离子表面活性剂具体的例子包括烷基化的萘磺酸酯的钠盐，亚甲基-二萘-二磺酸二钠，烷基苯磺酸钠，烷基苯氧基苯二磺酸钠，磺酸酯化的烷基-二苯醚，全氟烷基磺酸铵或者钾和二辛基-磺基琥珀酸钠。
非离子表面活性剂合适的例子包括聚氧乙烯烷基醚，聚氧乙烯烷基芳基醚，其中该芳基可以是苯基，萘基或者芳族杂环基团，聚氧乙烯聚苯乙烯基苯基醚，聚氧乙烯聚氧丙烯 烷基醚，聚氧乙烯聚氧丙烯嵌段聚合物，甘油脂肪族酸的偏酯，山梨聚糖脂肪族酸的偏酯，季戊四醇脂肪族酸的偏酯，丙二醇单脂肪族酯，蔗糖脂肪族酸的偏酯，聚氧乙烯山梨聚糖脂肪族酸的偏酯，聚氧乙烯山梨糖醇脂肪族酸的偏酯，聚乙二醇脂肪族酯，聚甘油脂肪族酸的偏酯，聚氧乙烯化的蓖麻油，聚氧乙烯甘油脂肪族酸的偏酯，脂肪族二乙醇酰胺，N，N-双-2-羟基烷基胺，聚氧乙烯烷基胺，三乙醇胺脂肪族酯，和三烷基氧化胺。在这些非离子表面活性剂中，特别优选的是聚氧乙烯烷基苯基醚，聚氧乙烯烷基萘基醚和聚氧乙烯-聚氧丙烯嵌段聚合物。
合适的非离子表面活性剂具体的例子包括山梨醇和/或脱水山梨醇脂肪酸酯的环氧乙烷加合物，聚丙二醇环氧乙烷加合物，二甲基硅氧烷-环氧乙烷嵌段共聚物，二甲基硅氧烷-(环氧丙烷-环氧乙烷)嵌段共聚物，和多元醇的脂肪酸酯。
阳离子表面活性剂不受特别限制，并且可以使用常规已知的阳离子表面活性剂。例如，烷基胺盐，季铵盐，聚氧乙烯烷基胺盐和聚乙烯聚胺衍生物。
可用于本发明的两性表面活性剂没有特殊限制，可使用传统公知的两性表面活性。可列举例如：氨基酸类、甜菜碱类、氧化胺类等的两性表面活性剂等。
此外，还可以使用炔二醇类的氧化乙烯加合物或炔醇类，或氟基、硅基等的表面活性剂。
两种或多种上述表面活性剂可以组合使用。例如，两种或多种不同的阴离子表面活性剂的组合或者阴离子表面活性剂与非离子表面活性剂的组合会是优选的。对这样的表面活性剂的量没有具体限制，但是优选为0.1至10重量％，更优选为0.1至5重量％。
本发明的显影液还可以含有水溶性聚合物化合物，示例有大豆多糖，改性淀粉，阿拉伯树胶，糊精，纤维素衍生物(例如，羧基甲基纤维素，羧基乙基纤维素或甲基纤维素)和其改性产物，支链淀粉，聚乙烯醇及其衍生物，聚乙烯基吡咯烷酮，聚丙烯酰胺，丙烯酰胺共聚物，乙烯基甲基醚/马来酸酐共聚物，乙酸乙烯酯/马来酸酐共聚物，苯乙烯/马来酸酐共聚物等。
在水溶性聚合物化合物中，特别优选大豆多糖，改性淀粉，阿拉伯树胶，糊精，羧基甲基纤维素，聚乙烯醇等。
水溶性聚合物化合物可以以两种以上的组合使用。在显影液中的水溶性聚合物化合物的含量优选为0.1至20重量％，更优选为0.5至10重量％。
除上述组分以外，在本发明中的显影液还可以含有消泡剂，有机酸，无机酸，无机盐等。
作为消泡剂，优选使用常规的硅氧烷基自乳化型或乳化型消泡剂，优选使用硅氧烷消泡剂。可以使用乳化分散型、溶解型等中的任何一种。消泡剂的含量优选为0.001至1.0重量％。
作为有机酸，示例有乙二胺四乙酸，柠檬酸，乙酸，草酸，丙二酸，水杨酸，辛酸，酒石酸，苹果酸，乳酸，乙酰丙酸，对甲苯磺酸，二甲苯磺酸，植酸，有机膦酸等。有机酸也可以以碱金属盐或铵盐的形式使用，如乙二胺四乙酸二钠盐。有机酸的含量优选为0.1至5重量％。
作为无机酸或无机盐，示例有磷酸，偏磷酸，磷酸二氢铵，磷酸氢二铵，磷酸二氢钠，磷酸氢二钠，磷酸二氢钾，磷酸氢二钾，三聚磷酸钠，焦磷酸钾，六偏磷酸钠，硝酸镁，硝酸钠，硝酸钾，硝酸铵，硫酸钠，硫酸钾，硫酸铵，亚硫酸钠，亚硫酸铵，硫酸氢钠，硫酸镍等。无机盐的含量优选为0.1至5重量％。
本发明中显影液的pH不受特别限制，只要其是表现出缓冲作用的pH即可，优选在6至11的范围内。并且特别优选在7至10的范围内。
印刷版前体：
本发明中使用的平版印刷版前体的特征在于具有如下的阴图型图像形成能力，即，图像曝光后的区域固化而形成图像部，未曝光部通过如上所述的显影处理而被除去，由此形成非图像部。
底基：
在本发明的平版印刷版前体中使用的底基，没有特别限定。只要底基具有亲水性表面，或至少具有比可成像层更加亲水性的表面即可。底基可以由常用于制备可成像元件例如平版印刷版的任何材料组成。它通常呈片材、膜或箔片(或网幅)形式，并且具有一定强度稳定性和延展性，在使用条件下能够抗尺寸变化以保证印刷时对色无误。通常底基可以是任何自撑材料，包括聚合物膜(例如聚酯、聚乙烯、聚碳酸酯、纤维素酯聚合物和聚苯乙烯膜)，玻璃，陶瓷，金属片或箔或刚性纸(包括树脂或金属涂覆的纸)或任何这些材料的叠片(例如铝箔叠到聚酯薄膜上的叠片)。金属支持体包括铝、铜、锌、钛和它们的合金的片材或箔片。
本发明特别优选的底基是使用本领域中已知技术的铝支持体构成，其制作方法，包括通过物理(机械)磨版、电化学磨版或化学磨版进行打磨粗化，接着采用酸性阳极氧化加以处理。有用的亲水性平版印刷底基是以电化学方式磨版并硫酸或磷酸阳极化的铝支持体。
铝支持体的硫酸阳极氧化一般在铝表面上产生1.5-5g/m 2，更通常是2.5-4g/m 2的氧化物(覆盖度)。而磷酸阳极氧化一般在铝表面上产生1-5g/m 2，更通常是1.5-3g/m 2的氧化物。 当采用硫酸阳极氧化时，更高的氧化物重量(至少3g/m 2)可以提供更长的印刷寿命。
经过阳极氧化的铝支持体还可以用例如硅酸盐、糊精、氟化钙锆、六氟硅酸、聚乙烯基膦酸(PVPA)、乙烯基膦酸共聚物、甲基丙烯酸或丙烯酸共聚物等材料处理以提高亲水性。
底基的厚度可以改变但是应该足以承受印刷的磨损和足够柔性以便卷绕。常用的厚度为0.1mm至多并包括0.7mm经处理的铝箔。
此外，底基材也可以是其上具有可成像层的圆柱形表面，比如是印刷机的组成部分。此种成像筒体的使用曾经在美国专利5，713，287(Gelbart)中进行了描述。
可成像涂层：
本发明所述的可成像涂层至少包含自由基可聚合化合物、光引发剂、粘结剂和显影促进剂的可成像组合物。另外，在本发明中，“底基上涂覆一种可成像组合物”是指可以在底基上以直接接触的方式设置辐射敏感组合物的涂层，也可以在底基与辐射敏感涂层之间或辐射敏感涂层之上设置其他层，并不否定依照期望设置在平版印刷版前体中的保护层、底涂层、中间层、背涂层等任意层的存在。
自由基可聚合化合物：
自由基可聚合化合物是本领域技术人员所公知的并在相当多文献中进行过描述，包括：“Photoreactive Polymers:The Science and Technology of Resists”，A.Reiser,Wiley,New York,1989，102-177页，B.M.Monroe；“Radiation Curing:Science and Technology”,S.P.Pappas,Ed.，Plenum,New York,1992,399-440页；“Polymer Imaging”,A.B.Cohen和P.Walker；“Imaging Processes ana Material”,I.M.Sturge等人，Van Nostrand Reinhold,New York，1989，226-262页。另外，有用的自由基可聚合的组分还描述在欧洲专利1,182,033(Fujimaki等人)。
根据本发明，自由基可聚合化合物是含有至少一个烯类不饱双键的聚合单体或寡聚体，可优选自多元醇的丙烯酸酯、多元醇的甲基丙烯酸酯、氨酯丙烯酸酯、氨酯甲基丙烯酸酯、环氧化物丙烯酸酯、环氧化物甲基丙烯酸酯、聚氨酯丙烯酸酯、聚氨酯甲基丙烯酸酯、聚醚丙烯酸酯、聚醚甲基丙烯酸酯中的一种或多种。
合适的自由基可聚合单体可以包括例如，多官能丙烯酸酯单体或多官能甲基丙烯酸酯单体(例如乙二醇，三羟甲基丙烷，季戊四醇，乙氧基化的乙二醇，乙氧基化的三羟甲基丙烷的丙烯酸酯，乙氧基化的三羟甲基丙烷的甲基丙烯酸酯，多官能氨基甲酸酯化的丙烯酸酯，多官能氨基甲酸酯化的甲基丙烯酸酯，环氧化的丙烯酸酯，和环氧化的甲基丙烯酸 酯)，和低聚胺二丙烯酸酯。除了丙烯酸酯基团、甲基丙烯酸酯基团之外，丙烯酸单体或甲基丙烯酸单体也可以具有其他双键或者环氧化物基团。该丙烯酸单体或甲基丙烯酸单体还可以包含酸(例如羧酸)或者碱(例如胺)官能度。有用的自由基可聚合化合物包括多官能氨基甲酸酯化的丙烯酸酯、聚氨酯丙烯酸酯、季戊四醇四丙烯酸酯和对本领域技术人员显而易见的其它可聚合单体。
自由基可聚合的组分按足以使得UV辐射敏感性组合物在辐射曝光之后不溶于水性显影剂的量存在于该组合物中。这一般为25-65重量％，通常30-60重量％，基于辐射敏感性组合物的干重。
光引发剂：
用于本发明中的自由基光引发剂展现UV-紫光范围内的一个或多个吸收频带，并且这些频带中的至少一个延伸至所示电磁谱的所述可见范围中，或在所述可见范围内具有肩部或一个或多个其它次要频带。例如鎓盐、三卤甲基化合物、羰基化合物、叠氮化合物、香豆素、酮基香豆素、蒽醌、有机硼化合物、肟酯或氧化膦中的一种或多种。
合适的鎓盐包括锍鎓盐、氧亚砜鎓盐、氧鎓盐、亚砜鎓盐、膦鎓盐、重氮盐、卣鎓盐如碘鎓盐。具体实例包括氯化二苯基碘鎓、六氟磷酸二苯基碘鎓、六氟磷酸(4-甲基苯基)[4-(2-甲基丙基)-苯基]碘鎓、六氟磷酸双(4-叔丁基苯基)碘鎓、六氟锑酸二苯基碘鎓、辛基硫酸二苯基碘鎓、辛基硫代硫酸二苯基碘鎓、2-羧酸二苯基碘鎓、对甲苯磺酸N-甲氧基-a-甲基吡啶鎓、四氟硼酸4-甲氧基苯_重氮盐、氯化2-氰基乙基_三苯基膦鎓、双六氟磷酸双_[4-二苯基锍鎓苯基]硫醚、六氟锑酸双-4-十二烷基苯基碘鎗、六氟锑酸三苯基锍鎓、四氟硼酸三苯基锍鎓、辛基硫酸三苯基锍鎓、六氟锑酸苯氧基苯基重氮盐和六氟锑酸苯氨基苯基重氮盐。
光引发剂还包括三氯甲基三嗪类引发体系，如美国专利4,997,745中所述；二芳基碘鎓盐和光敏剂，如美国专利5,546,258中所述；用于可见光激活的光谱敏感剂和三氯甲基三嗪类，如美国专利5,599,650中所述；用于紫外线和可见光激活的3-酮香豆素类以及聚羧酸共引发剂，例如苯胺基-N，N-二乙酸和第二共引发剂，如美国专利5,942,372中所述；花青染料、二芳基碘鎓盐和具有经亚甲基与直接与芳环相连的N、O或S基团相连的羧酸基团的共引发剂，如美国专利5,368,990中所述。适用的自由基引发剂包括，例如，2-(4-甲氧苯基)-4,6-二(三氯甲基)-2-三嗪、2-(4-甲氧基-1-萘基)-4,6-二(三氯甲基)-1,3,5-三嗪、苯胺基-N,N-二乙酸、2，2-二甲氧基-2-苯基乙酞苯、2-甲基-l-[4-(甲基硫)苯基-2-吗啉基丙-l-酮、苯基双(2,4,6-三甲基苯甲酰基)氧化膦、3-苯甲酰基-7-甲氧基香豆素、香豆素酮93、二苯乙 醇酮或烷基取代的蒽醌、叔丁基铵丁基硼酸三苯和三苯基(正丁基)硼酸四乙铵。
包括一种或多种引发剂化合物的引发剂组合物按0.5-25％的量，优选至少1％且至多并包括20％的量存在于辐射敏感性组合物中，该用量基于辐射敏感性组合物的总固体或涂覆的可成像层的干重计。
粘结剂：
本发明的粘结剂为主链含碳的聚合物，可以没有限定地使用本领域中已知在阴图平版印刷版前体的感光层中使用的粘合剂聚合物等的任意一种或两种以上。
有用的聚合物粘结剂可以是匀质的，即溶解在涂料溶剂中，或可以作为离散颗粒存在并且包括但不限于丙烯酸、甲基丙烯酸、丙烯酸酯衍生出的聚合物、甲基丙烯酸酯衍生出的聚合物、聚乙烯基缩醛、酚醛类树脂、由苯乙烯及其衍生物、丙烯腈、甲基丙烯腈、N-取代环状酰亚胺或马来酸酐衍生出的聚合物，例如欧洲专利1,182,033(上面指出)和美国专利6，309，792(上面指出)、美国专利6，569，603(上面指出)和美国专利6，893，797(Munnelly等人)中描述的那些。还有用的是美国专利7，175,949(Tao等人)中描述的乙烯基咔唑聚合物。
另一方面，有用的聚合物粘结剂也可是分布(通常均匀地)在整个可成像层中的颗粒状聚合物。这些聚合物中具有颗粒直径在10-10，000nm(通常20-800nm)的平均粒度。通常该聚合物粘合剂在室温为固体，并且典型的是非弹性的热塑体。该聚合物粘合剂包含亲水和疏水区域二者，这被认为对于通过促进显影能力来提高曝光和未曝光区域的差异而言是重要的，该离散粒子的存在倾向于促进未曝光区域的显影能力。这种实施方案的聚合物粘合剂具体的例子描述在美国专利6，899，994(上面指出)、WO2009/030279(Andriessen等人)、美国专利7，261，998(Hayashi等人)、美国专利7，659，046(Munnelly等人)以及欧州专利1，614，540(Vermeersch等人)
除了以上实施方案的聚合物粘合剂之外，可成像层可以任选地包含一种或多种共粘合剂。典型的共粘合剂有，例如纤维素衍生物，聚乙烯醇，聚丙烯酸，聚甲基丙烯酸，聚乙烯基吡咯烷酮，聚交酯，聚乙烯基膦酸，合成的共聚物，例如烷氧基聚乙二醇丙烯酸酯的共聚物、烷氧基聚乙二醇甲基丙烯酸酯的共聚物。
用作粘合剂聚合物典型平均分子量为2000-500000，优选5000-100000。相对于组合物的非挥发性组分的总重量，所有粘合剂聚合物合计用量通常是10-60重量％，优选20-60重量％。
显影促进剂：
为了更有效地让可成像涂层同时实现“离机显影”和“在机显影”的效果，本发明可成像组合物中使用的显影促进剂为低分子量亲水性有机化合物或高分子量亲水性聚合物。
用作显影促进剂的低分子量亲水性有机化合物为多元醇以及它们的醚或酯衍生物、有机胺以及它们的盐、有机磺酸以及它们的盐的一种或多种。实例包括乙二醇、二甘醇、三甘醇、丙二醇、一缩二丙二醇和二缩三丙二醇、甘油、季戊四醇和三(2-羟乙基)异氰脲酸酯、三乙醇胺、二乙醇胺和单乙醇胺、甲苯磺酸，十二烷基苯磺酸钠、二丁基萘磺酸钠、二辛基琥珀酸磺酸钠、
Figure PCTCN2022084721-appb-000004
10L-45、乳化剂OS、
Figure PCTCN2022084721-appb-000005
3B2、
Figure PCTCN2022084721-appb-000006
ABL。
所述用作显影促进剂的高分子量亲水性聚合物为聚乙二醇、阿拉伯树胶，淀粉，纤维素，糊精，多糖，以及含有羧基、磺酸基、膦酸基团、酰胺基团、乙烯基吡咯烷酮单体的均聚物或者共聚物的一种或多种。
相对于可成像涂层的全部固体成分重量显影促进剂的添加量为1-20重量％，优选1-15重量％。
除此之外，本发明中所述组合物还可以按常规量包括各种添加剂，例如表面活性剂、着色染料、粘附力促进剂、对比度染料、阻聚剂、抗氧化剂或它们的组合，或常用于平版印刷技术的任何其它附加物。
印刷版前体的形成：
本发明可以通过将上述可成像组合物适当地施涂到上述的底基上形成具有可成像涂层的印刷版前体。具体地说，是将所述可成像组合物分散或溶解于适合的涂布溶剂中形成混合溶液，并采用适合的设备和程序如旋涂、刀涂、凹版涂布、模涂、狭槽涂布、棒涂、盘条涂布、辊涂或挤出机料斗涂布，将所述混合溶液施加到基材载体的表面上，也可以通过喷涂到适合的支持体如印刷机的印刷筒上来施加所述组合物，然后在70℃-160℃烘箱内干燥除去所述涂布溶剂，即得所述平版印刷印版前体。
作为在此所使用的溶剂的选择取决于所述组合物中的聚合物粘结剂及其它非聚合物组分的性质，通常在本领域中熟知的条件和技术下所使用的涂布溶剂，可以列举：丙酮、环己酮、甲醇、乙醇、丙醇、丁醇、甲基乙基酮、甲基异丁基酮、四氢呋喃、1-甲氧基-2-丙醇、2-乙氧基-乙醇、2-甲氧基乙基乙酸酯、1-甲氧基-2-丙基乙酸酯、二甲氧基乙烷、乳酸甲酯、乳酸乙酯、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、四甲基脲、N-甲基吡咯烷酮、二甲亚砜、γ-丁内脂等，但不限定于这些溶剂。溶剂可以单独使用一种或者混合使用两种以上。
干燥后的可成像层的涂层重量一般是至少0.l-5g/m 2，优选0.5-3g/m 2。
在本发明的平版印刷版前体中，为了防止脂肪、油、灰尘或氧化的污染及刮擦造成的损伤，还可优选在可成像涂层上设置包含一种或多种表面保护性化合物保护层。作为在保护层中可以使用的材料，可以适当选择水溶性聚合物、水不溶性聚合物的任一种来使用，还可根据需要混合使用两种以上。具体而言，可列举例如:阿拉伯树胶，支链淀粉，纤维素衍生物例如羧甲基纤维素，羧乙基纤维素或者甲基纤维素，糊精，环糊精，乙烯醇，聚乙烯醇，乙烯基吡咯烷酮，聚乙烯基吡咯烷酮，多糖，丙烯酸，甲基丙烯酸或者丙烯酰胺的均聚物和共聚物等。其中，优选使用结晶性较优异的水溶性高分子化合物，具体而言，将聚乙烯醇用作主成分时，能够给氧阻断性、显影除去性之类的基本特性带来最良好的结果。
曝光：
对于本发明的实施方案而言，用于将本发明的平版印刷印版前体曝光的激光可以是碳弧灯、高压水银灯、氙灯、金属卤化物灯、荧光灯、钨灯、卤素灯、氦镉激光、氩离子激光、FD—YAG激光、氦氖激光、半导体激光(350nm—450nm)对感光层进行图像曝光。目前可商购的图像数码制版机中使用的高性能激光器或激光二极管的发射波长为405nm，成像设备可以配置为平板式记录器或鼓式记录器，其中可成像元件安装到鼓的内或外圆柱表面。合适的曝光设备例如：CRON(科雷)和AMSKY(保利特)的CTCP/UV成像机、BasysPrint的Xeikon UV装置、Liischer的Xpose UV机、ECRM的Nautilius设备。取决于辐射感光层的感光度，一般采用30mJ/cm2至500mJ/cm2，优选50mJ/cm2至300mJ/cm2的能量进行该成像。
在曝光之后和显影之前，可根据需要对印版前体选择预热或不预热的处理。一般说来，经过显影前预热处理的印版能或多或少提高它的印刷耐印能力。最终通过前述的显影工序制得成像的平版印刷版被安装到印刷机上，涂覆印刷油墨和润版溶液进行印刷，其中润版溶液被未成像区域(由成像和冲洗步骤揭露的亲水性基材表面)吸收，并且油墨被成像层(未除去)区域吸收。然后将该油墨转移至适合的接收材料(例如布、纸、金属、玻璃或塑料)而在其上提供图像的所需压印。如果需要的话，可以使用中间“转印辊”来将油墨从成像构件转移到接收材料。
下面结合具体实施例对本发明提供的平版印刷版的制版方法进行详细说明。除非如下特别说明，实例中的大部分组分化合物可以从Aldrich Chemical Company(Milwaukee,WI)获得。
下述实施例中使用的一些特殊组分和材料如下：
粘结剂A是含90重量％苯乙烯和10重量％聚乙二醇甲醚甲基丙烯酸酯在丙醇/水(体积比 为80/20)中的聚合物分散体，固含量为23.7％。
粘结剂B是含80重量％的甲基丙烯酸甲酯和20重量％甲基丙烯酸的聚合物在2-丁酮中的溶液，浓度为33％。
粘结剂C是含92重量％甲基丙烯酸甲酯和8重量％聚乙二醇甲醚甲基丙烯酸酯在丙醇/水(体积比为80/20)中的聚合物分散体，固含量为24.0％。
粘结剂D是含20重量％苯乙烯、70重量％丙烯酸氰乙酯和10重量％聚乙二醇甲醚甲基丙烯酸酯在丙醇/水(体积比为80/20)中的聚合物分散体，固含量为23.8％。
粘结剂E是含90重量％的甲基丙烯酸烯丙酯和10重量％聚乙二醇甲醚甲基丙烯酸酯在2-丁酮中的聚合物溶液，固含量为10％。
自由基可聚合化合物A:1,6-己二异氰酸酯与丙烯酸羟乙酯和三丙烯酸季戊四醇酯的反应产物(在2-丁酮中的聚合物溶液，固含量为80％)。
Sartomer 355是多官能丙烯酸单体，得自Sartomer Co.,Inc。
PI-18是2-(4-甲氧基-1-萘基)-4,6-二(三氯甲基)-1,3,5-三嗪，可购自DKSH Group(Zurich,Switzerland)。
Figure PCTCN2022084721-appb-000007
250是(4-甲氧基苯基)[4-(2-甲基丙基)苯基]碘鎓六氟磷酸盐，可购自Ciba Specialty Chemicals(Tarrytown,NY)。
PI-0591是一种碘鎓盐引发剂，可购自日本东京化成工业株式会社。
BYK-341有机硅表面助剂，可购自德国毕克公司。
TMSPMA代表3-(甲基丙烯酰氧)-丙基三甲氧基硅烷。
显影液A是如下所制备的溶液：向750g的去离子水中，在搅拌下依次溶解：13g碳酸钠和7g碳酸氢钠；50g十二烷基苯磺酸钠；25g阿拉伯胶；50g乙二醇单苯基醚；20g对甲基苯磺酸；0.1g
Figure PCTCN2022084721-appb-000008
SE 47消泡剂；将去离子水进一步加入到l000g。显影液A的pH为8.9。
显影液B是如下所制备的溶液：向750g的去离子水中，在搅拌下依次溶解：25g碳酸氢钠和5g碳酸钠；50g正丁基萘磺酸钠；3.0g乙二胺四乙酸二钠；0.1g
Figure PCTCN2022084721-appb-000009
47消泡剂；将去离子水进一步加入到l000g。显影液B的pH为7.4。
实施例1
本实施例中所述的可成像组合物包括如下重量百分比：
Figure PCTCN2022084721-appb-000010
Figure PCTCN2022084721-appb-000011
将上述各成分溶解于20.2g的1-甲氧基-2-丙醇、9.5g的水和16.5g的2-丁酮的混合溶剂中，利用旋转涂布方法把溶液覆盖在经电化学粗化和阳极氧化处理得到的铝版基上，然后在110℃烘箱内干燥2min，即制得涂层重量为1.2g/m 2的平版印刷版前体。
这样得到的平版印刷版前体可通过CRON(科雷)的UVP-820G+型CTcP制版机上使用405nm激光器，转鼓旋转速度500rpm，激光功率45mW，进行图形扫描曝光后，在25℃温度下用上述显影液A通过MASTER VIEW显影机冲洗35s，得到良好的图像；也可选择直接将平版印刷版前体通过UV晒版机曝光，然后直接安装在印刷机上，打印出超过500张质量良好的印品。
实施例2
本实施例中所述的可成像组合物包括如下重量百分比：
Figure PCTCN2022084721-appb-000012
将上述各成分溶解于20.2g的1-甲氧基-2-丙醇、9.5g的水和16.5g的2-丁酮的混合溶剂中，利用旋转涂布方法把溶液覆盖在经电化学粗化和阳极氧化处理得到的铝版基上，然后在110 ℃烘箱内干燥2min，即制得涂层重量为1.2g/m 2的平版印刷版前体。
这样得到的平版印刷版前体可通过CRON(科雷)的UVP-820G+型CTcP制版机上使用405nm激光器，转鼓旋转速度500rpm，激光功率45mW，进行图形扫描曝光后，在25℃温度下用上述显影液A通过MASTER VIEW显影机冲洗35s，得到良好的图像；也可选择直接将平版印刷版前体通过UV晒版机曝光，然后直接安装在印刷机上，打印出超过500张质量良好的印品。
实施例3
本实施例中所述的可成像组合物包括如下重量百分比：
Figure PCTCN2022084721-appb-000013
将上述各成分溶解于20.2g的1-甲氧基-2-丙醇、9.5g的水和16.5g的2-丁酮的混合溶剂中，利用旋转涂布方法把溶液覆盖在经电化学粗化和阳极氧化处理得到的铝版基上，然后在110℃烘箱内干燥2min，得到的第一涂层重量为1.2g/m 2。然后用阿拉伯树胶(3.0g)和水(94.0g)的溶液覆盖第一层涂布上方，再次在110℃烘箱内干燥2min，即制备得到双涂层总重量约为2.2g/m 2的平版印刷印版前体。
这样得到的平版印刷版前体可通过CRON(科雷)的UVP-820G+型CTcP制版机上使用405nm激光器，转鼓旋转速度500rpm，激光功率45mW，进行图形扫描曝光后，在25℃温度下用上述显影液B通过MASTER VIEW显影机冲洗35s，得到良好的图像；也可选择直接将平版印刷版前体通过UV晒版机曝光，然后直接安装在印刷机上，打印出超过500张质量良好的印品。
实施例4
本实施例中所述的可成像组合物包括如下重量百分比：
Figure PCTCN2022084721-appb-000014
将上述各成分溶解于20.2g的1-甲氧基-2-丙醇、9.5g的水和16.5g的2-丁酮的混合溶剂中，利用旋转涂布方法把溶液覆盖在经电化学粗化和阳极氧化处理得到的铝版基上，然后在110℃烘箱内干燥2min，即制得涂层重量为1.2g/m 2的平版印刷版前体。
这样得到的平版印刷版前体可通过CRON(科雷)的UVP-820G+型CTcP制版机上使用405nm激光器，转鼓旋转速度500rpm，激光功率45mW，进行图形扫描曝光后，在25℃温度下用上述显影液B通过MASTER VIEW显影机冲洗35s，得到良好的图像；也可选择直接将平版印刷版前体通过UV晒版机曝光，然后直接安装在印刷机上，打印出超过500张质量良好的印品。
实施例5
本实施例中所述的可成像组合物包括如下重量百分比：
Figure PCTCN2022084721-appb-000015
将上述各成分溶解于20.2g的1-甲氧基-2-丙醇、9.5g的水和16.5g的2-丁酮的混合溶剂中， 利用旋转涂布方法把溶液覆盖在经电化学粗化和阳极氧化处理得到的铝版基上，然后在110℃烘箱内干燥2min，得到的第一涂层重量为1.2g/m 2。然后用聚乙烯醇(3.0g)和水(94.0g)的溶液覆盖第一层涂布上方，再次在110℃烘箱内干燥2min，即制备得到双涂层总重量约为2.1g/m 2的平版印刷印版前体。
这样得到的平版印刷版前体可通过CRON(科雷)的UVP-820G+型CTcP制版机上使用405nm激光器，转鼓旋转速度500rpm，激光功率45mW，进行图形扫描曝光后，在25℃温度下用上述显影液A通过MASTER VIEW显影机冲洗35s，得到良好的图像；也可选择直接将平版印刷版前体通过UV晒版机曝光，然后直接安装在印刷机上，打印出超过500张质量良好的印品。
显然，上述实施例仅仅是为清楚地说明所作的举例，而并非对实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引伸出的显而易见的变化或变动仍处于本发明创造的保护范围之中。

Claims (10)

  1. 一种用于光敏阴图型平版印刷版的可成像组合物，其特征在于包括如下质量份数的组分：
    Figure PCTCN2022084721-appb-100001
    其中，所述自由基可聚合化合物为含有至少一个烯类不饱双键的可聚合单体和/或寡聚体；
    所述光引发剂在UV-紫光范围内具有一个或多个吸收峰或吸收肩带；
    所述粘结剂为主链含碳的聚合物；
    所述显影促进剂为低分子量亲水性有机化合物或高分子量亲水性聚合物。
  2. 根据权利要求1所述的可成像组合物，其特征在于：所述光引发剂对波长范围在350nm-450nm的辐射线敏感。
  3. 根据权利要求1所述的可成像组合物，其特征在于：所述可聚合单体和/或寡聚体为丙烯酸酯、甲基丙烯酸酯、氨酯丙烯酸酯、氨酯甲基丙烯酸酯、环氧化物丙烯酸酯或环氧化物甲基丙烯酸酯、多元醇的丙烯酸酯、多元醇的甲基丙烯酸酯、聚氨酯丙烯酸酯、聚氨酯甲基丙烯酸酯、聚醚丙烯酸酯、聚醚甲基丙烯酸酯中的一种或多种。
  4. 根据权利要求1所述的可成像组合物，其特征在于：所述光引发剂为鎓盐、三卤甲基化合物、羰基化合物、叠氮化合物、香豆素、酮基香豆素、蒽醌、有机硼化合物、肟酯或氧化膦中的一种或多种。
  5. 根据权利要求1所述的可成像组合物，其特征在于：所述主链含碳的聚合物为丙烯酸、甲基丙烯酸、丙烯酸酯、甲基丙烯酸酯、丙烯酰胺、甲基丙烯酰胺、苯乙烯及苯乙烯衍生物、丙烯腈、甲基丙烯腈、N-取代环状酰亚胺、马来酸酐中的至少一种构成重复单元而衍生出的聚合物。
  6. 根据权利要求1所述的可成像组合物，其特征在于：所述主链含碳的聚合物的平均分子量为5000-100000。
  7. 根据权利要求1中所述的可成像组合物，其特征在于：所述用作显影促进剂的低分子量亲水性有机化合物为多元醇以及它们的醚或酯衍生物、有机胺以及它们的盐、有机磺酸以及它们的盐；所述用作显影促进剂的高分子量亲水性聚合物为聚乙二醇、阿拉伯树胶，淀粉，纤维素，糊精，多糖，以及含有羧基、磺酸基、膦酸基团、酰胺基团、乙烯基吡咯烷酮单体的均聚物或者共聚物。
  8. 一种光敏阴图型平版印刷版的制版方法，其特征在于：包括如下步骤：
    (1)在具有亲水表面或亲水层的底基上涂覆权利要求1-6任一项所述的可成像组合物得到光敏阴图型平版印刷版前体；
    (2)图案化曝光所述平版印刷版前体，从而形成曝光区域和未曝光区域；
    (3)将已曝光的印刷版前体通过显影工序除去所述未曝光区域获得所需的平版印刷版，所述显影工序为如下的任意一种：(i)在机显影：使用润版溶液和/或平版印刷油墨在印刷机上实施显影；(ii)离机显影：使用一种显影液在印刷机外的冲版机中实施显影。
  9. 根据权利要求8所述的制版方法，其特征在于：所述用于离机显影的显影液包含碳酸盐和/或碳酸氢盐，所述显影液中碳酸盐和/或碳酸氢盐的质量分数为1-20％，所述显影液的pH值为6–11。
  10. 根据权利要求9所述的制版方法，其特征在于：所述显影液中碳酸盐为碱金属碳酸盐；所述显影液中碳酸氢盐为碱金属碳酸氢盐。
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