CN113954502B - Photosensitive negative-working lithographic printing plate precursor and method for making lithographic printing plate by using the same - Google Patents

Photosensitive negative-working lithographic printing plate precursor and method for making lithographic printing plate by using the same Download PDF

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Publication number
CN113954502B
CN113954502B CN202111248592.5A CN202111248592A CN113954502B CN 113954502 B CN113954502 B CN 113954502B CN 202111248592 A CN202111248592 A CN 202111248592A CN 113954502 B CN113954502 B CN 113954502B
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printing plate
lithographic printing
parts
development
plate precursor
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CN113954502A (en
Inventor
翁银巧
高邈
徐能平
应作挺
常士旺
潘枫
马显瑶
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 PCT/CN2022/084722 priority patent/WO2023071054A1/en
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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
    • 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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/32—Liquid compositions therefor, e.g. developers
    • G03F7/322—Aqueous alkaline compositions

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Manufacturing & Machinery (AREA)
  • Printing Plates And Materials Therefor (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)

Abstract

The invention discloses a photosensitive negative-working lithographic printing plate precursor and a platemaking method using the same to form a lithographic printing plate, the lithographic printing plate precursor comprises: (i) An aluminum plate substrate, the surface of which is covered with a hydrophilic layer containing phosphate/fluoride, wherein the hydrophilic layer comprises the following components in parts by mass: 90-99.8 parts of phosphate and 0.2-10 parts of fluoride; (ii) Applying an imageable coating to the hydrophilic layer surface of said aluminum plate substrate, said imageable coating comprising the following parts by mass of an imageable composition: 25-65 parts of free radical polymerizable compound, 0.5-25 parts of photoinitiator, 10-60 parts of binder and 1-20 parts of developing accelerator. The plate making method comprises the following steps: (1) Exposing the lithographic printing plate precursor with a laser in a desired image to form exposed and unexposed areas; (2) The unexposed regions are removed from the exposed printing plate precursor by a development process to produce the desired lithographic printing plate. Flexible development processes of "on-press development" or "off-press development" can be achieved with the imageable compositions and platemaking methods described above, and the resulting printing plates have excellent printing properties.

Description

Photosensitive negative-working lithographic printing plate precursor and method for making lithographic printing plate by using the same
Technical Field
The invention belongs to the technical field of lithographic printing plate preparation, and particularly relates to a photosensitive negative lithographic printing plate precursor and other plate making methods.
Background
Recent developments in the field of lithographic printing plates have led to widespread use of digitization techniques for electronically processing, storing, and outputting image information by computers, and various new image output methods corresponding to such digitization techniques have been put into practical use. This creates a computer-to-plate (CTP) technique in which digitized image information can be supported by a highly focused radiation beam such as a laser beam, and the lithographic printing plate precursor is directly subjected to scanning exposure using the laser beam. Such a technique attracts attention because of its advantage of making a lithographic printing plate without using a conventional film, and is one of the important technical subjects in the field of lithographic printing plates.
In the conventional process for producing a lithographic printing plate, a process step of removing an unnecessary photosensitive coating by dissolution in a developer after exposure is required, which causes a relative time and an increase in cost. In particular, in recent years, disposal of waste liquid discharged in association with development treatment with a strongly alkaline solution has become a subject of great attention in the entire industry from the viewpoint of environmental protection. Therefore, as a problem of further simplifying the plate making process and reducing the waste water disposal, various new techniques including a printing plate precursor which can be mounted on a machine without chemical development after exposure or a manufacturing process capable of off-machine development with a near-neutral aqueous solution have been a challenge in technical research in the field of today.
As one of plate-making techniques satisfying the challenges described above, a CTP printing plate precursor called "on-press development" or "treatment-free" and a plate-making method thereof have been proposed, which is capable of removing an unexposed portion of an image-recording layer by mechanical contact of ink and/or fountain solution on a printing press through a rotating cylinder to obtain a lithographic printing plate. The treatment-free CTP plate has obvious energy-saving and emission-reducing advantages, and firstly, the treatment-free CTP plate does not need to use a chemical reagent for special treatment, so that the high cost caused by flushing is saved, and the cost for purchasing the chemical reagent and related instruments and the maintenance cost are saved. And secondly, the treatment-free CTP plate does not need to be flushed by chemical liquid, a processing procedure is omitted compared with the traditional CTP plate, the production process flow is simplified, the operation is simpler and more convenient, and the production and preparation time is saved.
Another solution to simplify the process and to solve the waste solution problem is to use near neutral aqueous solutions for development, a platemaking process also known as "low chemistry processing". This method has the advantage over the "process-free" techniques described above of being able to detect the quality of the image after exposure and before the printing press and of avoiding contamination of the unexposed areas of the plate by ambient light. EP 1342568 discloses a method of making a heat-sensitive CTP lithographic printing plate such that a thermal imaging precursor comprising hydrophobic thermoplastic polymer particles which coalesce when heated can be developed with a protective gum solution. EP1751625 provides a method for manufacturing lithographic plates from photopolymer CTP plate precursors, the exposed plate being a simplified process where development with resist and gumming occur simultaneously in a single bath. Because the unexposed areas of the photopolymer plate are removed by the gumming step, the exposed plate can be stored in ambient light for a long time before it is mounted on the press and can provide a visible image before the plate is mounted on the press. Furthermore, the treatment with the resist gives better cleaning than the treatment with fountain solution and ink on the press.
The field of CTP lithographic printing plates has developed over decades with two main trends, thermal and light sensing, the thermal sensing technology using near infrared (830 nm wavelength) laser imaging and the light sensing technology using ultraviolet and visible (380-405 nm wavelength) laser imaging. Chinese patent document CN106313870B discloses a method for preparing a heat-sensitive negative pattern CTP lithographic printing plate, which adopts a plate making method that directly puts on a printing machine for development imaging after exposure, or puts on the printing machine after exposure and low-chemical development imaging, so as to realize off-machine development and on-machine development, and meet the requirement of customers to select a more practical method according to actual conditions.
At present, the market of chemical treatment-free heat-sensitive CTP (computer to plate) lithographic printing plates at home and abroad is expanding year by year, but the chemical treatment-free light-sensitive lithographic printing plates are still limited to low chemical treatment technology in the field of Violet laser (Violet), and the development of the light-sensitive treatment-free lithographic printing plates in the field of ultraviolet light (UV) is still a blank. The on-press development or treatment-free CTP lithographic printing plate in the photosensitive field is not applied in the market, and is seriously lagged behind the heat-sensitive CTP lithographic printing plate technology in the aspects of implementing environment-friendly plate making and controlling the development of wastewater discharge. Therefore, research and development of the chemical treatment-free photosensitive CTP lithographic printing plate is a necessary trend for adapting to green printing and energy-saving and environment-friendly policies, and has a very positive significance.
The lower energy required to expose a uv-light negative-working CTP-lithographic printing plate relative to a heat-sensitive negative-working CTP-lithographic printing plate requires a design that increases the sensitivity of the imageable composition to the conversion from hydrophilic to oleophilic. The invention adopts polyfunctional carbamated acrylate or polyfunctional carbamated methacrylate with high crosslinking density to prepare a free radical polymerizable compound through condensation reaction of components such as diisocyanate, polyol, hydroxyethyl (methyl) acrylate and the like; a photoinitiator capable of rapidly generating free radical crosslinking under ultraviolet radiation and a development promoter with high latitude are selected to improve the photosensitive speed and the imaging function; the main component of the hydrophilic coating on the substrate is screened to form a phosphate/fluoride-containing material, so that the combination of the photosensitive layer and the plate base of the digital printing plate is firmer after the digital printing plate is scanned by a photosensitive plate making machine, and the printing endurance and the exposure speed of the printing plate are improved. Thereby achieving the breakthrough in the ultraviolet negative pattern treatment-free CTP lithographic printing plate technology.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defects that a large amount of corrosive developing solution is generated in the plate making process of the photosensitive CTP lithographic printing plate and the actual developing process is single, so that the flexible developing process which can be developed on-line as well as off-line is provided, and the photosensitive CTP lithographic printing plate precursor and the plate making method thereof which meet the actual requirements of customers are realized.
The present invention provides a photosensitive negative-working lithographic printing plate precursor comprising: (i) An aluminum plate substrate having a hydrophilic phosphate/fluoride-containing layer formed on the surface thereof; (ii) An imageable coating is applied to the hydrophilic layer surface of the aluminum plate substrate.
The phosphate/fluoride hydrophilic layer comprises the following components in parts by mass:
90-99.9 parts of phosphate
0.1 to 10 portions of fluoride
The imageable coating comprises the following imageable composition in parts by mass:
25-65 parts of free radical polymerizable compound,
0.5 to 25 portions of light initiator,
10-60 parts of a binder,
1-20 parts of a developing accelerator.
The lithographic printing plate precursor is sensitive to radiation having a wavelength in the range of 350nm to 450 nm.
The aluminum plate substrate is preferably an aluminum support that is electrochemically grained and anodized by sulfuric acid.
The phosphate in the phosphate/fluoride hydrophilic layer is one or more of alkali metal phosphate, alkali metal hydrogen phosphate and alkali metal dihydrogen phosphate; the fluoride is one or more of alkali metal fluoride, alkali metal fluorophosphate, alkali metal fluoroaluminate, alkali metal fluorotantalate, alkali metal fluoroantimonate, alkali metal fluorozirconate, alkali metal fluoroarsenate and alkali metal fluoroborate.
Preferably, the phosphate is one or more of potassium dihydrogen phosphate and sodium dihydrogen phosphate; the fluoride is one or more of potassium fluoride, sodium fluoride, potassium fluoroaluminate and sodium fluoroaluminate.
The free radical polymerizable compound is a polymerized monomer and/or oligomer containing at least one ethylenically unsaturated double bond;
the photoinitiator has one or more absorption peaks or absorption shoulder bands in the UV-violet range;
the binder is a polymer with a carbon-containing main chain;
the development accelerator is a low molecular weight hydrophilic organic compound or a high molecular weight hydrophilic polymer.
Preferably, the polymeric monomer and/or oligomer is one or more of acrylate, methacrylate, urethane acrylate, urethane methacrylate, epoxide acrylate or epoxide methacrylate, acrylate of polyol, methacrylate of polyol, urethane acrylate, urethane methacrylate, polyether acrylate, polyether methacrylate.
Preferably, the photoinitiator is one or more of an onium salt, a trihalomethyl compound, a carbonyl compound, an azide compound, a coumarin, a ketocoumarin, an anthraquinone, an organoboron compound, an oxime ester or a phosphine oxide.
Preferably, the polymer containing carbon in the main chain is derived from repeating units composed of at least one of acrylic acid, methacrylic acid, acrylate, methacrylate, acrylamide, methacrylamide, styrene and styrene derivatives, acrylonitrile, methacrylonitrile, N-substituted cyclic imide, and maleic anhydride.
Preferably, the average molecular weight of the polymer containing carbon in the main chain is 5000-100000.
Preferably, the low-molecular weight hydrophilic organic compound used as a development accelerator is a polyhydric alcohol and an ether or ester derivative thereof, an organic amine and a salt thereof, an organic sulfonic acid and a salt thereof; the high molecular weight hydrophilic polymer used as the developing accelerator is one or more of polyethylene glycol, gum arabic, starch, cellulose, dextrin, polysaccharide, and homopolymer or copolymer containing carboxyl, sulfonic acid, phosphonic acid, amide, and vinyl pyrrolidone monomers.
The invention also provides a plate making method of the photosensitive negative-type lithographic printing plate, which comprises the following steps:
(1) Pattern-wise exposing a light-sensitive negative-working lithographic printing plate precursor to form exposed and unexposed regions;
(2) Removing the unexposed areas of the exposed printing plate precursor by a developing process to obtain the desired lithographic printing plate, the developing process being any one of: (i) on-press development: performing development on the press using a fountain solution and/or lithographic printing ink; (ii) off-press development: the development is carried out in a plate processor outside the printing press using a developer solution.
Wherein the photosensitive negative-working lithographic printing plate precursor comprises: (i) An aluminum plate substrate having a hydrophilic phosphate/fluoride-containing layer formed on the surface thereof; (ii) An imageable coating is applied to the hydrophilic layer surface of the aluminum plate substrate.
The phosphate/fluoride hydrophilic layer comprises the following components in parts by mass:
90-99.9 parts of phosphate
0.1 to 10 portions of fluoride
The imageable coating comprises the following imageable composition in parts by mass:
25-65 parts of free radical polymerizable compound,
0.5 to 25 portions of light initiator,
10-60 parts of a binder, namely,
1-20 parts of a developing accelerator.
Wherein 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 shoulder bands in the UV-violet range;
the binder is a polymer with a carbon-containing 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 comprises carbonate and/or bicarbonate, the mass fraction of the carbonate and/or bicarbonate in the developing solution is 1-20%, and the pH value of the developing solution is 6-11.
Preferably, the carbonate in the developer is an alkali metal carbonate; the bicarbonate in the developing solution is alkali metal bicarbonate.
Further, the 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.
Further, the developing solution also comprises at least one of a surfactant and/or a water-soluble high molecular compound.
The mass concentration of the surfactant in the developing solution is 0.1-10%;
the mass concentration of the water-soluble high molecular compound in the developing solution is 0.1-20%;
the pH value of the developing solution is preferably 7-10.
The step (2) further includes, before the developing step, a step of performing a pre-heating process on the printing plate precursor after the exposure.
Further, the imageable coating can comprise one or more layers.
The invention also provides a photosensitive negative-type lithographic printing plate prepared by the plate making method.
Compared with the prior art, the technical scheme of the invention has the following advantages:
1) The photosensitive negative-type lithographic printing plate precursor provided by the invention has the advantages that the combination of a photosensitive layer and a plate base is firmer after a digital printing plate is scanned by a photosensitive plate making machine by regulating the types and the contents of components in an aluminum plate substrate and an imageable coating and the hydrophilic coating on the substrate contains phosphate/fluoride materials, the multifunctional carbamated (methyl) acrylate containing high crosslinking density is adopted, a photoinitiator capable of quickly generating free radical crosslinking under ultraviolet radiation and a development accelerator with high latitude are selected, so that the exposure light speed and the imaging function are improved, the CTP lithographic printing plate making process in the photosensitive field is more environment-friendly and safer, various development processes can be effectively adapted, and a client can be ensured to flexibly select the development processes according to actual requirements, such as 'off-machine development' and 'on-machine development', and the final development effect cannot be damaged by selecting different development processes.
2) According to the plate making method of the photosensitive negative planographic printing plate, provided by the invention, the developing solution mainly contains carbonate and bicarbonate in the off-press developing process, and does not contain high-corrosivity alkaline substances, so that the discharge of waste liquid is reduced; and carbonate ions and bicarbonate ions, exhibit a buffering action and can prevent fluctuation of pH even when the developing solution is used for a long time. Therefore, deterioration of developing performance, occurrence of development scum, and the like, which are caused by fluctuation of pH, are suppressed.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific embodiments. This invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete and will fully convey the concept of the invention to those skilled in the art, and the present invention will only be defined by the appended claims.
The term "off-press development" in the present invention refers to a step of removing the image-recording layer of a lithographic printing plate precursor by contact with a liquid (usually a developer solution) in an apparatus (usually an automatic plate processor), thereby exposing the surface of the hydrophilic support; the term "on-press development" refers to a step of removing the image-recording layer of a lithographic printing plate precursor by contact with ink and/or fountain solution on a printing press, thereby exposing the surface of a hydrophilic support; the term "process-free" refers to a platemaking process that does not require any mechanical or chemical treatment after exposure and prior to being placed on press, unless otherwise specified.
Hereinafter, the CTP lithographic printing plate precursor and the plate making method of the present invention will be described in detail. First, the development step, which is the most characteristic step, will be described, and then the other steps will be described.
And a developing process:
the plate making method of the lithographic printing plate of the present invention comprises: removing the unexposed regions of the exposed printing plate precursor by a development process, with or without a pre-heat step, wherein the development process is any of: (i) on-press development: performing the developing process on a printing press using a fountain solution and/or a lithographic printing ink; (ii) off-press development: the development process is carried out in a plate processor outside the printing press using a neutral or weakly alkaline developer solution comprising carbonate and/or bicarbonate.
a. On-press development:
the printing plate precursors of the present invention are "on-press developable," for example, by mounting the printing plate precursor directly to a printing press, rotating the plate cylinder while fountain solution and/or ink is supplied to the imageable coating of the printing plate precursor. After many revolutions of the plate cylinder, preferably less than 50 revolutions, the non-exposed areas of the imageable coating are removed from the support, wherein the non-exposed areas in the imageable coating can be removed by a suitable fountain solution, lithographic ink, or a combination of both, in any order during printing.
In a preferred embodiment, only fountain solution is supplied to the printing plate at the very start of the press, and then the ink supply is started after a few revolutions of the apparatus.
In an alternative embodiment, the fountain solution and ink supply can be started simultaneously as soon as the press is started, or only ink is supplied to the plate at the start, and then after a few revolutions of the apparatus.
In yet another alternative embodiment, on-press processing can be accomplished by supplying a single fluid ink to the printing plate. Single fluid inks consist of an ink phase (also known as a hydrophobic or oleophilic phase) and a polar phase that replaces the aqueous fountain solution used in conventional offset printing. Examples of suitable single fluid inks are described in U.S. patent nos. 4, 045, 232; U.S. patent 4,981,517 and U.S. patent 6,140,392. In a most preferred embodiment, the single fluid ink comprises an ink phase and a polyol phase, as described in WO 00/32705.
Such a developing process avoids the use of conventional alkaline developers and the use of separate developing equipment.
And off-machine development:
the off-press development treatment of the present invention is not particularly limited, and development may be performed by a known method. Development can be accomplished using so-called "manual" development, "immersion" development, or rinsing with an automatic developing device (typically a rinser). In the case of "manual" development, the entire imaging member is sanded with a sponge or cotton pad sufficiently impregnated with a suitable developer (described below), followed by rinsing with water to effect development. "Dip" development involves immersing the imaged element in a stirred tank or pan containing a suitable developer for 10-60 seconds (especially 20-40 seconds), followed by rinsing with water, with or without sanding with a sponge or cotton pad. The use of automatic developing devices is well known and generally involves pumping developer into a developing tank and then spraying it from a spray nozzle. The imaging member is contacted with the developer in a suitable manner. The apparatus may also include a suitable grinding mechanism (e.g. a brush or roller) and a suitable number of feed rollers. Some developing apparatuses include a laser exposure device and the apparatus is divided into an image forming section and a developing section. For example, the developer solution (or developer) may be applied to the imaging member as follows: sanding, spraying, dipping, immersion, slot coating 125254 (see, e.g., fig. I and 2 of Maruyama et al, U.S. patent 6,478,483) or reverse roll coating (as described in fig. 4 of Kurui et al, U.S. patent 5,887,214), or wiping the outer layer with a rinse solution or contacting it with a roll, dip pad or applicator containing the sizing. For example, the imaging member can be brushed with a rinse solution, or it can be poured onto the imaging surface or developed by spraying the imaging surface with sufficient force to remove the unexposed areas using a spray nozzle system such as described in EP1, 788, 431 and U.S. patent 6, 992, 688 (Shimazu et al). Also, the imaging member may be immersed in a rinsing solution and sanded manually or with equipment.
Suitable off-press development apparatuses have at least one roller for abrading or brushing the imaged element while applying the developer solution. By using such a processing apparatus, the plate can be made to more completely and quickly remove the unexposed areas of the imaging layer. The residual developer can be removed (e.g., using a squeegee or nip rollers) or left on the resulting printing plate without any rinsing step. Excess developer can be collected in the tank and used several times and replenished from a reservoir if necessary. The developer replenisher may be of the same concentration as the developer used in the rinse, or provided in concentrated form and diluted with water at the appropriate time. The developing process may be performed with a fresh liquid all the time, but it is preferable that the developing liquid after the developing treatment is circulated through a filter and reused. The filter for filtering the developer used in the developing step may be any filter as long as it can filter foreign matter mixed in the developer. As a material of the filter, polyester resin, polypropylene resin, polyethylene resin, cellulose resin, cotton, or the like is preferably used. The mesh pore size of the filter is preferably 5-500 μm, more preferably 10-200 μm, further preferably 20-100 μm.
The off-press development step of the present invention is preferably performed by an automatic processor equipped with a rubbing member in which the image-exposed lithographic printing plate precursor is subjected to a rubbing treatment while being conveyed; automatic processing machines such as those described in us patents 5, 148, 746 and 5, 568, 768 and british patents 2, 297, 719, particularly preferred are those that use rotating brush rollers as the rubbing members. As the rotating brush roller, a known rotating brush roller manufactured by inserting brush wires in a plastic or metal roller may be used. As a material of the brush, a plastic fiber (e.g., polyester-based, e.g., polyethylene terephthalate or polybutylene terephthalate, polyamide-based, e.g., nylon 6.6 or nylon 6.10, polyacrylic-based, e.g., polyacrylonitrile or polyalkyl (meth) acrylate, and polyolefin-based, e.g., polypropylene or polystyrene) may be used. For example, a brush material having a fiber hair diameter of 20 to 400 μm and a hair length of 5 to 30mm may be preferably used. The outer diameter of the rotating brush roller is preferably 30 to 200mm, and the peripheral speed of the brush at the rubbing plate surface is preferably 0.1 to 5 m/sec.
The rotation direction of the rotating brush rollers may be the same direction or an opposite direction with respect to the conveying direction of the planographic printing plate precursor, but when 2 or more rotating brush rollers are used, it is preferable that at least one rotating brush roller rotates in the same direction and at least one rotating brush roller rotates in an opposite direction with respect to the conveying direction. With such a configuration, the non-image area of the photosensitive layer is more stably removed.
In the plate-making method of a lithographic printing plate of the present invention, a conventional three-bath development system can be employed,
the three-bath developing system is a method for sequentially performing three treatment steps, i.e., an off-machine developing step, a water washing step, and a gumming step, and has at least 3 types of treatment baths, in which treatment liquids in the respective baths are used for performing the respective treatment steps. The plate-making method of the lithographic printing plate of the present invention may be performed by using only the developing step with the developer as a treatment step, i.e., by using a single treatment bath (also referred to as a single bath treatment), without performing the water washing step and the gumming step before and after the off-press developing step.
After the off-press development process, the resulting lithographic printing plate can be placed on a cylinder of a printing press and printing is performed by applying ink and fountain solution to the printing side of the imaged and developed element.
In the present invention, the drying step may be optionally provided after the developing step. In particular, it is preferable to set the process at the last step of the automatic processing machine.
Developing solution:
the developing solution used in the plate making method of a lithographic printing plate of the present invention is a neutral or weakly alkaline aqueous solution or aqueous dispersion containing at least a carbonate, a bicarbonate, or a combination of both. In view of the presence of carbonate ions and bicarbonate ions, a buffering action is exhibited and fluctuation of pH can be prevented even when the developing solution is used for a long time. Therefore, deterioration of developing performance, occurrence of development scum, and the like, which are caused by fluctuations in pH, are suppressed. In order to allow carbonate ions and bicarbonate ions to be present in the developing solution at the same time, the present invention preferably uses a combination of carbonate and bicarbonate, or carbonate ions and bicarbonate ions may be generated by adding carbonate to the developing solution and then adjusting the pH. The carbonate or bicarbonate used is not particularly limited, and is preferably an alkali metal salt thereof. As the alkali metal salt, lithium carbonate, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium carbonate, and potassium hydrogen carbonate are exemplified; sodium carbonate, sodium hydrogencarbonate, potassium carbonate and potassium hydrogencarbonate are preferred, and sodium carbonate and sodium hydrogencarbonate are particularly preferred. 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 from 1 to 20 wt%, more preferably from 3 to 15 wt%, based on the weight of the aqueous developing solution.
The developer of the present invention may also contain a surfactant (e.g., an anionic, nonionic, cationic or amphoteric surfactant).
Examples of the anionic surfactant include ricinoleic acid esters (aliphates), abietic acid esters, hydroxyalkane sulfonates, alkane sulfonates, dialkyl sulfosuccinates, linear alkylbenzene sulfonates, branched alkylbenzene sulfonates, alkyl naphthalene sulfonates, alkylphenoxypolyoxyethylene propyl sulfonates, salts of polyoxyethylene alkyl sulfophenyl ethers, sodium N-methyl-N-oleyl taurate, disodium monoamide N-alkyl sulfosuccinate, petroleum sulfonates, sulfated castor oil, sulfated tallow, sulfuric ester salts of aliphatic alkyl esters, salts of alkyl sulfates, sulfuric esters of polyoxyethylene alkyl ethers, sulfuric ester salts of aliphatic monoglycerides, sulfuric ester salts of polyoxyethylene alkyl phenyl ethers, sulfuric ester salts of polyoxyethylene styryl phenyl ethers, salts of alkyl phosphorus esters, phosphoric ester salts of polyoxyethylene alkyl ethers, phosphoric ester salts of polyoxyethylene alkyl phenyl ethers, partially saponified compounds of styrene maleic anhydride copolymers, partially saponified compounds of olefin-maleic anhydride copolymers, and naphthalene sulfonate formalin condensates. Among these anionic surfactants, dialkyl sulfosuccinates and alkyl naphthalene sulfonates are particularly preferred.
Specific examples of suitable anionic surfactants include sodium salts of alkylated naphthalene sulfonates, disodium methylene-dinaphthalene-disulfonates, sodium alkylbenzenesulfonates, sodium alkylphenoxyphenyldisulfonates, sulfonated alkyl-diphenyl ethers, ammonium or potassium perfluoroalkyl sulfonates, and sodium dioctyl-sulfosuccinates.
Suitable examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, wherein the aryl group may be a phenyl group, a naphthyl group or an aromatic heterocyclic group, polyoxyethylene polystyrene phenyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene polyoxypropylene block polymers, partial esters of glycerol fatty acids, partial esters of sorbitan fatty acids, partial esters of pentaerythritol fatty acids, propylene glycol mono-fatty esters, partial esters of sucrose fatty acids, partial esters of polyoxyethylene sorbitan fatty acids, partial esters of polyoxyethylene sorbitol fatty acids, polyethylene glycol fatty esters, partial esters of polyglycerol fatty acids, polyoxyethylated castor oils, partial esters of polyoxyethylene glycerol fatty acids, aliphatic diethanolamides, N, N-bis-2-hydroxyalkylamines, polyoxyethylene alkylamines, triethanolamine fatty esters, and trialkylamine oxides. Among these nonionic surfactants, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkylnaphthyl ethers and polyoxyethylene-polyoxypropylene block polymers are particularly preferred.
Specific examples of suitable nonionic surfactants include ethylene oxide adducts of sorbitol and/or sorbitan fatty acid esters, polypropylene glycol ethylene oxide adducts, dimethyl siloxane-ethylene oxide block copolymers, dimethyl siloxane- (propylene oxide-ethylene oxide) block copolymers, and fatty acid esters of polyhydric alcohols.
The cationic surfactant is not particularly limited, and conventionally known cationic surfactants can be used. For example, alkylamine salts, quaternary ammonium salts, polyoxyethylene alkylamine salts and polyethylene polyamine derivatives.
The amphoteric surfactant which can be used in the present invention is not particularly limited, and conventionally known amphoteric surfactants can be used. Examples thereof include: amphoteric surfactants such as amino acids, betaines and amine oxides.
Further, an ethylene oxide adduct of an acetylene glycol, an acetylene alcohol, a fluorine-based or silicon-based surfactant, or the like can be used.
Two or more of the above surfactants may be used in combination. For example, a combination of two or more different anionic surfactants or a combination of an anionic surfactant and a nonionic surfactant 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 developing solution of the present invention may further contain a water-soluble polymer compound exemplified by soybean polysaccharide, modified starch, gum arabic, dextrin, cellulose derivatives (e.g., carboxymethyl cellulose, carboxyethyl cellulose or methyl cellulose) and modified products thereof, pullulan, polyvinyl alcohol and derivatives thereof, polyvinylpyrrolidone, polyacrylamide, acrylamide copolymer, vinyl methyl ether/maleic anhydride copolymer, vinyl acetate/maleic anhydride copolymer, styrene/maleic anhydride copolymer and the like.
Among the water-soluble polymer compounds, soybean polysaccharide, modified starch, gum arabic, dextrin, carboxymethyl cellulose, polyvinyl alcohol and the like are particularly preferable.
The water-soluble polymer compound 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 developing solution in the present invention may contain, in addition to the above components, a defoaming agent, an organic acid, an inorganic salt, and the like.
As the defoaming agent, a conventional silicone-based self-emulsifying or emulsifying-type defoaming agent is preferably used, and a silicone defoaming agent is preferably used. Any of emulsion dispersion type, dissolution type, and the like can be used. The content of the defoaming agent is preferably 0.001 to 1.0% by weight.
As the organic acid, ethylenediamine tetraacetic 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, an organic phosphonic acid, and the like are exemplified. The organic acids may also be used in the form of alkali metal or ammonium salts, such as disodium ethylenediaminetetraacetate. The content of the organic acid is preferably 0.1 to 5% by weight.
As the inorganic acid or inorganic salt, phosphoric acid, metaphosphoric acid, monoammonium phosphate, diammonium hydrogen phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, monopotassium phosphate, dipotassium hydrogen phosphate, sodium tripolyphosphate, potassium pyrophosphate, sodium hexametaphosphate, magnesium nitrate, sodium nitrate, potassium nitrate, ammonium nitrate, sodium sulfate, potassium sulfate, ammonium sulfate, sodium sulfite, ammonium sulfite, sodium hydrogen sulfate, nickel sulfate, and the like are exemplified. The content of the inorganic salt is preferably 0.1 to 5% by weight.
The pH of the developing solution in the present invention is not particularly limited as long as it is a pH showing a buffering action, and is preferably in the range of 6 to 11. And particularly preferably in the range of 7 to 10.
Printing plate precursor:
the lithographic printing plate precursor used in the present invention is characterized by having a negative image forming ability in which an image-exposed region is cured to form an image portion, and an unexposed portion is removed by the development treatment as described above to form a non-image portion.
A base:
the base used in the lithographic printing plate precursor of the present invention is composed of an aluminum plate support, and the production method thereof comprises roughening by physical (mechanical) graining, electrochemical graining, or chemical graining, followed by treatment with acid anodizing. The preferred hydrophilic lithographic printing plate base of the present invention is an electrochemically grained and sulfuric acid anodized aluminum plate support.
Sulfuric acid anodization of aluminum supports typically produces 1.5-5g/m on the aluminum surface 2 More usually 2.5-4 g/m 2 Oxide (coverage). Higher oxide weights (at least 3 g/m) when sulfuric acid is used for anodization 2 ) A longer print life may be provided.
The anodized aluminum plate support may further have its oxide layer coated with a phosphate/fluoride-containing material to increase hydrophilicity. The invention preferably covers a hydrophilic layer containing sodium dihydrogen phosphate and sodium fluoride, wherein the hydrophilic layer comprises the following components in parts by mass: 90-99.9 parts of sodium dihydrogen phosphate and 0.1-10 parts of sodium fluoride.
The thickness of the substrate can vary but should be sufficient to withstand the wear of the printing and flexible enough to be rolled. Commonly used thicknesses are 0.1 mm up to and including 0.7 mm treated aluminium foil.
Alternatively, the base substrate may be a cylindrical surface having an imageable layer thereon, such as is part of a printing press. The use of such an imaging cylinder has been described in us patent 5,713,287 (Gelbart).
Imageable coating:
the imageable coating of this invention comprises at least an imageable composition of a free radical polymerizable compound, a photoinitiator, a binder, and a development promoter. In addition, in the present invention, "an imageable coating is applied on the surface of the hydrophilic layer of the aluminum plate base" means that a coating of the radiation-sensitive composition can be provided on the base in direct contact, and other layers can be provided between the base and the radiation-sensitive coating or on the radiation-sensitive coating, without negating the presence of any of the layers such as a protective layer, an undercoat layer, an intermediate layer, and a back coat layer, which are provided in the lithographic printing plate precursor as desired.
Free radical polymerizable compounds：
Free radical polymerizable compounds are well known to those skilled in the art and are described in considerable literature, including: "Photoactive Polymers The Science and Technology of Resists", A.Reiser, wiley, new York,1989, pages 102-177, B.M. Monroe; "Radiation Curing: science and Technology", S.P. Pappas, ed., plenum, new York,1992, pages 399-440; "Polymer Imaging", a.b. Cohen and p.walker; "Imaging Processes and materials", I.M. Sturge et al, van Nostrand Reinhold, new York,1989, pages 226-262. In addition, useful free-radically polymerizable components are described in European patent 1, 182,033 (Fujimaki et al).
According to the invention, the radically polymerizable compound is a polymerizable monomer or oligomer containing at least one ethylenically unsaturated double bond, which may preferably be selected from one or more of the group consisting of acrylates of polyols, methacrylates of polyols, urethane acrylates, urethane methacrylates, epoxide acrylates, epoxide methacrylates, urethane acrylates, urethane methacrylates, polyether acrylates, polyether methacrylates.
Suitable free radically polymerizable monomers can include, for example, multifunctional acrylate monomers or multifunctional methacrylate monomers (e.g., ethylene glycol, trimethylolpropane, pentaerythritol, ethoxylated ethylene glycol, ethoxylated trimethylolpropane acrylates, ethoxylated trimethylolpropane methacrylates, multifunctional urethanized acrylates, multifunctional urethanized methacrylates, epoxidized acrylates, and epoxidized methacrylates), and oligomeric amine diacrylates. In addition to acrylate groups, methacrylate groups, acrylic monomers or methacrylic monomers can also have further double bonds or epoxide groups. The acrylic or methacrylic monomers may also include acid (e.g., carboxylic acid) or base (e.g., amine) functionalities. Useful free radically polymerizable compounds include multifunctional urethane acrylates, pentaerythritol tetraacrylate, and other polymerizable monomers that will be apparent to those skilled in the art.
The free-radically polymerizable component is present in the UV radiation-sensitive composition in an amount sufficient to render the composition insoluble in an aqueous developer after radiation exposure. This is generally from 25 to 65% by weight, usually from 30 to 60% by weight, based on the dry weight of the radiation-sensitive composition.
Photoinitiator(s)：
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, or has a shoulder or one or more other secondary bands within the visible range. For example one or more of an onium salt, a trihalomethyl compound, a carbonyl compound, an azide compound, a coumarin, a ketocoumarin, an anthraquinone, an organoboron compound, an oxime ester or a phosphine oxide.
Suitable onium salts include sulfonium salts, sulfoxonium salts, oxonium salts, sulfoxonium salts, phosphonium salts, diazonium salts, and onium salts with high valency, such as iodonium salts. Specific examples include diphenyliodonium chloride, diphenyliodonium hexafluorophosphate, (4-methylphenyl) [4- (2-methylpropyl) -phenyl ] iodonium hexafluorophosphate, bis (4-tert-butylphenyl) iodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium octylsulfate, diphenyliodonium octylthiosulfate, diphenyliodonium 2-carboxylate, N-methoxy-a-picolinium p-toluenesulfonate, 4-methoxybenzenediazonium tetrafluoroborate, 2-cyanoethyltriphenylphosphonium chloride, bis [ 4-diphenylsulfonium phenyl ] sulfide bis hexafluoroantimonate, bis-4-dodecylphenyliodonium hexafluoroantimonate 37783, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium octylsulfate, phenoxyphenyl diazonium hexafluoroantimonate and anilinophenylphenyl diazonium hexafluoroantimonate.
Photoinitiators also include trichloromethyl triazine-based initiation systems, as described in U.S. Pat. No. 4,997,745; diaryliodonium salts and photosensitizers as described in U.S. Pat. No. 5,546,258; spectral sensitizers and trichloromethyl triazines for visible light activation, as described in U.S. patent No. 5,599,650; 3-ketocoumarins and polycarboxylic acid co-initiators for ultraviolet and visible light activation, such as anilino-N, N-diacetic acid and secondary co-initiators, as described in U.S. patent No. 5,942,372; cyanine dyes, diaryliodonium salts, and coinitiators having a carboxylic acid group attached via a methylene group to an N, O or S group attached directly to an aromatic ring, as described in U.S. patent No. 5,368,990. Suitable free-radical initiators include, for example, 2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) -2-triazine, 2- (4-methoxy-1-naphthyl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, anilino-N, N-diacetic acid, 2-dimethoxy-2-phenylethanephthalate, 2-methyl-l- [4- (methylthio) phenyl-2-morpholinopropan-l-one, phenylbis (2, 4, 6-trimethylbenzoyl) phosphine oxide, 3-benzoyl-7-methoxycoumarin, coumarone 93, benzil ketone or alkyl-substituted anthraquinone, triphenylphosphonium tert-butylammonium borate and tetraethylammonium triphenyl (N-butyl) borate.
The initiator composition comprising one or more initiator compounds is present in the radiation-sensitive composition in an amount of from 0.5 to 25%, preferably at least 1% and up to and including 20%, based on the total solids of the radiation-sensitive composition or the dry weight of the coated imageable layer.
Binder：
The binder of the present invention is a polymer containing carbon in the main chain, and any one or two or more of binder polymers and the like known in the art to be used in a photosensitive layer of a negative-working lithographic printing plate precursor can be used without limitation.
Useful polymeric binders may be homogeneous, i.e., dissolved in the coating solvent, or may exist 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 U.S. Pat. No. 6,309,792 (noted above), U.S. Pat. No. 6,569,603 (noted above), and U.S. Pat. No. 6,893,797 (Munnelly et al). Also useful are the vinylcarbazole polymers described in U.S. Pat. No. 7,175,949 (Tao et al).
On the other hand, useful polymeric binders can also be particulate polymers that are distributed (typically uniformly) throughout the imageable layer. These polymers have an average particle size with a particle diameter of 10-10,000 nm (usually 20-800 nm). The polymeric binder is generally a 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 to enhance the difference between exposed and unexposed regions by facilitating the developability, the presence of the discrete particles tending to facilitate the developability of the unexposed regions. Specific examples of polymeric binders of this embodiment are described in U.S. Pat. No. 6,899,994 (noted above), WO2009/030279 (Andriessen et al), U.S. Pat. No. 7,261,998 (Hayashi et al), U.S. Pat. No. 7,659,046 (Munnelly et al), and European patent 1,614,540 (Vermeersch et al)
In addition to the polymeric binders of the above embodiments, the imageable layer can optionally include one or more co-binders. Typical co-binders are, for example, cellulose derivatives, polyvinyl alcohols, polyacrylic acids, polymethacrylic acids, polyvinylpyrrolidone, polylactides, polyvinylphosphonic acids, synthetic copolymers, for example copolymers of alkoxy polyethylene glycol acrylates, copolymers of alkoxy polyethylene glycol methacrylates.
The average molecular weight of the polymers used as binders is typically in the range from 2000 to 500000, preferably from 5000 to 100000. The total amount of all binder polymers used together is generally from 10 to 60% by weight, preferably from 20 to 60% by weight, relative to the total weight of the non-volatile components of the composition.
Developing accelerator：
In order to more effectively allow the imageable coating to achieve both the "off-press development" and "on-press development" effects, the development accelerator used in the imageable coating of the present invention is a low molecular weight hydrophilic organic compound or a high molecular weight hydrophilic polymer.
The low molecular weight hydrophilic organic compound used as a development accelerator is one or more of polyhydric alcohols 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, glycerol, pentaerythritol and tris (2-hydroxyethyl) isocyanurate, triethanolamine, diethanolamine and monoethanolamine, toluene sulfonic acid, sodium dodecyl benzene sulfonate, dibutyl naphthalene sulfonate, dioctyl sodium succinate sulfonate, calfax 10L-45, emulsifier OS, DOWFAX 3B2, NAXAN ABL.
The high molecular weight hydrophilic polymer used as the developing accelerator is one or more of polyethylene glycol, gum arabic, starch, cellulose, dextrin, polysaccharide, and homopolymer or copolymer containing carboxyl, sulfonic acid, phosphonic acid, amide, and vinyl pyrrolidone monomers.
The development promoter is added in an amount of 1 to 20 wt%, preferably 1 to 15 wt%, relative to the total solids content of the imageable coating.
In addition, the compositions of the present invention may include various additives such as surfactants, coloring dyes, adhesion promoters, contrast dyes, polymerization inhibitors, antioxidants, or combinations thereof, or any other addenda commonly used in lithographic printing techniques, in conventional amounts.
Formation of printing plate precursor:
the present invention can form a printing plate precursor having an imageable coating by suitably applying the imageable composition described above to the aluminum plate substrate described above. Specifically, the lithographic printing plate precursor is prepared by dispersing or dissolving the imageable composition in a suitable coating solvent to form a mixed solution, and applying the mixed solution to the surface of a substrate carrier using suitable equipment and procedures such as spin coating, knife coating, gravure coating, die coating, slot coating, bar coating, wire rod coating, roll coating, or extruder hopper coating, or by spray coating onto a suitable support such as the printing cylinder of a printing press, followed by oven drying at 70 ℃ to 160 ℃ to remove the coating solvent.
The choice of solvent used herein depends on the nature of the polymeric binder and other non-polymeric components in the composition, and coating solvents generally used under conditions and techniques well known in the art, and may be exemplified by: 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-dimethylformamide, N-dimethylacetamide, tetramethylurea, N-methylpyrrolidone, dimethyl sulfoxide, γ -butyrolactone, and the like, but is not limited to these solvents. The solvent may be used singly or in combination of two or more.
The coating weight of the dried imageable layer is generally at least 0.l to 5g/m 2 Preferably 0.5 to 3g/m 2 。
In the lithographic printing plate precursor of the present invention, in order to prevent contamination by fats, oils, dust or oxidation and damage by scratching, it is also preferable to provide a protective layer comprising one or more surface protective compounds on the imageable coating. As the material that can be used for the protective layer, any of a water-soluble polymer and a water-insoluble polymer can be appropriately selected and used, and two or more kinds can be mixed and used as necessary. Specific examples thereof include gum arabic, pullulan, cellulose derivatives such as carboxymethyl cellulose, carboxyethyl cellulose or methyl cellulose, dextrin, cyclodextrin, vinyl alcohol, polyvinyl alcohol, vinyl pyrrolidone, polyvinyl pyrrolidone, polysaccharides, homopolymers and copolymers of acrylic acid, methacrylic acid or acrylamide, and the like. Among them, a water-soluble polymer compound having relatively excellent crystallinity is preferably used, and specifically, when polyvinyl alcohol is used as a main component, the most favorable results can be obtained for basic characteristics such as oxygen blocking property and development removability.
Exposure:
for the embodiment of the present invention, the laser used for exposing the lithographic printing plate precursor of the present invention may be a carbon arc lamp, a high pressure mercury lamp, a xenon lamp, a metal halide lamp, a fluorescent lamp, a tungsten lamp, a halogen lamp, a helium-cadmium laser, an argon ion laser, an FD-YAG laser, a helium-neon laser, a semiconductor laser (350 nm to 450 nm) for image-exposing the photosensitive layer. The emission wavelength of high performance lasers or laser diodes used in currently commercially available digital plate makers for images is 405nm, and the imaging device can be configured as a flatbed recorder or drum recorder, with the imageable element mounted to the inner or outer cylindrical surface of the drum. Suitable exposure apparatuses are, for example: CTCP/UV imagers from CRON and AMSKY, xeikonUV devices from Basysprint, xpos UV machines from Liischer, nautilus equipment from ECRM. Depending on the sensitivity of the radiation-sensitive layer, the imaging is generally carried out with an energy of from 30 mJ/cm2 to 500 mJ/cm2, preferably from 50 mJ/cm2 to 300mJ/cm 2.
After exposure and before development, a pre-heat or non-pre-heat treatment may be selected for the printing plate precursor as desired. Generally, a plate that has been pre-heat treated prior to development will have a greater or lesser increase in its print durability. The final imaged lithographic printing plate produced by the aforementioned development process is mounted on a printing press and printed by applying printing ink and fountain solution, wherein the fountain solution is absorbed by the non-imaged areas (hydrophilic substrate surface revealed by the imaging and development steps) and the ink is absorbed by the (non-removed) areas of the imaged layer. The ink is then transferred to a suitable receiving material (e.g., cloth, paper, metal, glass, or plastic) to provide the desired impression of the image thereon. If desired, an intermediate "transfer roller" may be used to transfer ink from the imaging member to the receiving material.
The plate making method of the lithographic printing plate according to the present invention will be described in detail with reference to specific examples. Most of the component compounds in the examples were available from Aldrich Chemical Company (Milwaukee, wis.), unless otherwise specified below.
Some of the specific components and materials used in the examples below are as follows:
binder A was a polymer dispersion containing 90% by weight styrene and 10% by weight polyethylene glycol methyl ether methacrylate in propanol/water (80/20 by volume) and a solids content of 23.7%.
Binder B was a 33% strength solution of a polymer containing 80% by weight of methyl methacrylate and 20% by weight of methacrylic acid in 2-butanone.
The binder C was a polymer dispersion containing 92% by weight of methyl methacrylate and 8% by weight of methoxypolyethylene glycol methacrylate in propanol/water (volume ratio 80/20) and a solids content of 24.0%.
The binder D was a polymer dispersion containing 20% by weight of styrene, 70% by weight of cyanoethyl acrylate and 10% by weight of polyethylene glycol methyl ether methacrylate in propanol/water (volume ratio 80/20) with a solids content of 23.8%.
The binder E was a polymer solution containing 90% by weight of allyl methacrylate and 10% by weight of methoxypolyethylene glycol methacrylate in 2-butanone and had a solids content of 10%.
The reaction product of 1, 6-hexamethylene diisocyanate, hydroxyethyl acrylate and pentaerythritol triacrylate (polymer solution in 2-butanone, solids content 80%) was used as free-radically polymerizable compound A.
Sartomer 355 is a multifunctional acrylic monomer available from Sartomer co.
PI-18 is 2- (4-methoxy-1-naphthyl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, available from DKSH Group (Zurich, switzerland).
Irgacure 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, available from Tokyo chemical industries, japan.
BYK-341 Silicone surface adjuvant, available from Bick, germany.
TMSPMA stands for 3- (methacryloyloxy) -propyltrimethoxysilane.
The aluminum plate substrate A is prepared by the following steps: degreasing the aluminum plate in an alkaline solution, performing electrochemical plate grinding and coarsening in an acidic solution, neutralizing in the alkaline solution, performing anodic oxidation in an acid solution, performing post-anodization treatment by using a hydrophilic solution, and finally drying in hot air to obtain the aluminum plate. In an embodiment, this step includes cleaning the aluminum plate at 65 ℃ with an alkaline aqueous solution containing sodium hydroxide (3.85 g/l) and sodium gluconate (good. 95 g/l) to remove any organic oils and greases from the surface thereof; followed by neutralization using, for example, an aqueous hydrochloric acid solution (2.og/1); and finally washed with water to remove excess hydrochloric acid solution. Subsequently, the aluminum plate was subjected to electrolytic roughening using a carbon electrode at 25 ℃ in an aqueous electrolyte containing aqueous hydrochloric acid (8.0 g/l) and acetic acid (16 g/l). The current and charge density were 38 OA/dm2 and 70.0C/dm 2, respectively. After roughening, the aluminum plate was ashed with aqueous sodium hydroxide solution (2.5 g/l) to remove unwanted impurities prior to anodization, and thereafter neutralized with aqueous sulfuric acid solution (2 g/l); and washed with water to remove excess acid. Subsequently, the aluminum plate is subjected to anodic oxidation, thereby producing an aluminum oxide layer. Anodization may occur at 25 ℃ in an aqueous electrolyte containing sulfuric acid (140 g/l); the current and charge density are adjusted to produce a charge having a charge density of about 2.5 and about 3.5g/m 2 In betweenA thick layer of aluminum oxide. Subsequently, the plate substrate was washed with water, treated with an aqueous solution containing sodium dihydrogen phosphate (50 g/l) and sodium fluoride (0.8 g/l) at 75 ℃ to enhance the hydrophilicity of the surface, finally washed with water at 50 ℃ and dried with hot air to obtain the desired aluminum plate substrate.
Developer a is a solution prepared as follows: to 750g of deionized water, dissolve successively with stirring: 13g sodium carbonate and 7g sodium bicarbonate; 50g of sodium dodecylbenzenesulfonate; 25g of acacia gum; 50g ethylene glycol monophenyl ether; 20g of p-toluenesulfonic acid; 0.1g SILFOAM SE 47 antifoaming agent; deionized water was further added to l000g. The pH of developer A was 8.9.
Developer B is a solution prepared as follows: to 750g of deionized water, dissolve successively with stirring: 25 Sodium bicarbonate and sodium carbonate 5 g; 50g sodium n-butylnaphthalene sulfonate; 3.0 g, disodium ethylene diamine tetraacetate; 0.1g SILFOAM SE 47 antifoaming agent; deionized water was further added to l000g. The pH of developer B was 7.4.
Example 1
The imageable composition described in this example includes the following weight percentages:
binder A3.53 g
Free radical polymerizable Compound A3.74 g
Sartomer 355 0.78 g
2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) -2-triazine 0.42 g
anilino-N, N-diacetic acid 0.23g
Polyethylene glycol 0.07 g
Brilliant blue BO 0.005g
TMSPMA 0.005 g
BYK-307 0.02 g
Dissolving the above components in a mixed solvent of 20.2g of 1-methoxy-2-propanol, 9.5g of water and 16.5g of 2-butanone, coating the solution on an aluminum plate substrate A obtained by electrochemical roughening, anodic oxidation and hydrophilic layer treatment of phosphate/fluoride by spin coating, and drying in an oven at 110 deg.C for 2min to obtain a coating with a weight of 1.2 g/m 2 A lithographic printing plate precursor of (1).
The lithographic printing plate precursor thus obtained was subjected to pattern scanning exposure using a 405nm laser, a drum rotation speed of 500rpm, and a laser power of 45mW on a CRON UVP-820G + -type CTcP plate making machine, and then washed with the above-mentioned developer A at a temperature of 25 ℃ for 35 s using a MASTER VIEW developing machine to obtain a good image; alternatively, the lithographic printing plate precursor is directly exposed through a UV printer and then directly mounted on a printing press to print over 500 good quality prints.
Example 2
The imageable composition described in this example includes the following weight percentages:
binder A2.22 g
Radical polymerizable Compound A2.44 g
Sartomer 355 0.51 g
Diphenyliodonium chloride 0.29 g
anilino-N, N-diacetic acid 0.23g
Coumarin ketone 93.06g
Polyacrylic acid 0.08 g
Brilliant blue BO 0.005g
TMSPMA 0.005 g
BYK-307 0.02 g
Dissolving the above components in a mixed solvent of 20.2g of 1-methoxy-2-propanol, 9.5g of water and 16.5g of 2-butanone, coating the solution on an aluminum plate substrate A obtained by electrochemical roughening, anodic oxidation and hydrophilic layer treatment of phosphate/fluoride by spin coating, and drying in an oven at 110 deg.C for 2min to obtain a coating with a weight of 1.2 g/m 2 A lithographic printing plate precursor of (1).
The lithographic printing plate precursor thus obtained was subjected to pattern scanning exposure using a 405nm laser, a drum rotation speed of 500rpm, and a laser power of 45mW on a CRON UVP-820G + -type CTcP plate making machine, and then washed with the above-mentioned developer A at a temperature of 25 ℃ for 35 s using a MASTER VIEW developing machine to obtain a good image; alternatively, the lithographic printing plate precursor is directly exposed by a UV printer and then directly mounted on a printing press to print over 500 good quality prints.
Example 3
The imageable composition described in this example included the following weight percentages:
binder A0.6 g
Binder E1.98 g
3.25 g of radically polymerizable Compound A
Irgacure 250 0.32 g
Tert-butylammonium butyl Borate triphenyl (0.28 g)
Mercaptotriazole 0.18g
Polyethylene glycol 0.07 g
Brilliant blue BO 0.005g
TMSPMA 0.005 g
BYK-307 0.02 g
Dissolving the above components in a mixed solvent of 20.2g of 1-methoxy-2-propanol, 9.5g of water and 16.5g of 2-butanone, coating the solution on an aluminum plate substrate A obtained by electrochemical roughening, anodic oxidation and phosphate/fluoride hydrophilic layer treatment by spin coating, and drying in an oven at 110 deg.C for 2min to obtain a first coating weight of 1.2 g/m 2 . The top of the first layer was then covered with a solution of gum arabic (3.0 g) and water (94.0 g) and dried again in an oven at 110 ℃ for 2min to produce a double coating having a total weight of about 2.2 g/m 2 A lithographic printing plate precursor of (1).
The lithographic printing plate precursor thus obtained was subjected to pattern scanning exposure using a 405nm laser on a UVP-820G + type CTcP plate making machine of CRON (korea), a drum rotation speed of 500rpm, a laser power of 45mW, and then washed with the above-mentioned developer B at a temperature of 25 ℃ for 35 seconds by a MASTER VIEW developer to obtain a good image; alternatively, the lithographic printing plate precursor is directly exposed through a UV printer and then directly mounted on a printing press to print over 500 good quality prints.
Example 4
The imageable composition described in this example included the following weight percentages:
binder C2.60 g
Binder B0.78 g
3.25 g of radically polymerizable Compound A
PI-0591 0.40 g
PI-18 0.18 g
Polyethylene glycol 0.08 g
Brilliant blue BO 0.005g
TMSPMA 0.005 g
BYK-307 0.02 g
Dissolving the above components in a mixed solvent of 20.2g of 1-methoxy-2-propanol, 9.5g of water and 16.5g of 2-butanone, coating the solution on an aluminum plate substrate A obtained by electrochemical roughening, anodic oxidation and phosphate/fluoride hydrophilic layer treatment by a spin coating method, and drying in an oven at 110 deg.C for 2min to obtain a coating with a weight of 1.2 g/m 2 A lithographic printing plate precursor of (1).
The lithographic printing plate precursor thus obtained was subjected to pattern scanning exposure using a 405nm laser, a drum rotation speed of 500rpm, and a laser power of 45mW on a CRON UVP-820G + -type CTcP plate making machine, and then washed with the above-mentioned developer B at a temperature of 25 ℃ for 35 s using a MASTER VIEW developing machine to obtain a good image; alternatively, the lithographic printing plate precursor is directly exposed by a UV printer and then directly mounted on a printing press to print over 500 good quality prints.
Example 5
The imageable composition described in this example included the following weight percentages:
binder D2.22 g
Radical polymerizable Compound A2.44 g
Sartomer 355 0.51 g
Bis (4-tert-butylphenyl) iodonium hexafluorophosphate 0.29 g
0.05g of phenylbis (2, 4, 6-trimethylbenzoyl) phosphine oxide
Arabic gum 0.08 g
Brilliant blue BO 0.005g
TMSPMA 0.005 g
BYK-307 0.02 g
Dissolving the above components in 20.2g of 1-methoxy-2-propaneThe solution was coated on an aluminum plate substrate A obtained by treating an electrochemically roughened, anodized, phosphate/fluoride hydrophilic layer by spin coating in a mixed solvent of alcohol, 9.5g of water and 16.5g of 2-butanone, followed by drying in an oven at 110 ℃ for 2min to obtain a first coating weight of 1.2 g/m 2 . Then covering the top of the first layer with a solution of polyvinyl alcohol (3.0 g) and water (94.0 g), and drying again in an oven at 110 deg.C for 2min to obtain a double coating with a total weight of about 2.1 g/m 2 A lithographic printing plate precursor of (1).
The lithographic printing plate precursor thus obtained was subjected to pattern scanning exposure using a 405nm laser, a drum rotation speed of 500rpm, and a laser power of 45mW on a CRON UVP-820G + -type CTcP plate making machine, and then washed with the above-mentioned developer A at a temperature of 25 ℃ for 35 s using a MASTER VIEW developing machine to obtain a good image; alternatively, the lithographic printing plate precursor is directly exposed by a UV printer and then directly mounted on a printing press to print over 500 good quality prints.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.

Claims (11)

1. A photosensitive negative-working lithographic printing plate precursor characterized by comprising: (i) An aluminum plate substrate having a hydrophilic phosphate/fluoride-containing layer formed on the surface thereof; (ii) Applying an imageable coating to the hydrophilic layer surface of said aluminum plate substrate;
the phosphate/fluoride hydrophilic layer comprises the following components in parts by mass:
90-99.9 parts of phosphate;
0.1-10 parts of fluoride;
the imageable coating comprises the following imageable composition in parts by mass:
25-65 parts of a free radical polymerizable compound;
0.5-25 parts of a photoinitiator;
10-60 parts of a binder;
1-20 parts of a developing accelerator;
the free radical polymerizable compound is a polymerizable monomer and/or oligomer containing at least one alkene unsaturated double bond;
the photoinitiator has one or more absorption peaks or absorption shoulder bands in the UV-violet range;
the binder is a polymer with a carbon-containing main chain;
the developing accelerant is a low molecular weight hydrophilic organic compound or a high molecular weight hydrophilic polymer;
the polymerizable monomer and/or oligomer is one or more of acrylate, methacrylate, urethane acrylate, urethane methacrylate, epoxide acrylate or epoxide methacrylate, acrylate of polyol, methacrylate of polyol, urethane acrylate, urethane methacrylate, polyether acrylate and polyether methacrylate.
2. The lithographic printing plate precursor according to claim 1, characterized in that: sensitive to radiation in the wavelength range 350 nm-450 nm.
3. The lithographic printing plate precursor according to claim 1, characterized in that: the aluminum plate substrate is an aluminum support which is electrochemically grained and anodized by sulfuric acid.
4. The lithographic printing plate precursor according to claim 1, characterized in that: the phosphate in the phosphate/fluoride hydrophilic layer is one or more of alkali metal phosphate, alkali metal hydrogen phosphate and alkali metal dihydrogen phosphate; the fluoride is one or more of alkali metal fluoride salt, alkali metal fluorophosphate, alkali metal fluoroaluminate, alkali metal fluorotantalate, alkali metal fluoroantimonate, alkali metal fluorozirconate, alkali metal fluoroarsenate and alkali metal fluoroborate.
5. The lithographic printing plate precursor according to claim 1, characterized in that: the photoinitiator is one or more of onium salt, trihalomethyl compound, carbonyl compound, azide compound, coumarin, ketocoumarin, anthraquinone, organoboron compound, oxime ester or phosphine oxide.
6. The lithographic printing plate precursor according to claim 1, characterized in that: the polymer containing carbon in the main chain is derived from at least one of acrylic acid, methacrylic acid, acrylic ester, methacrylic ester, acrylamide, methacrylamide, styrene and styrene derivatives, acrylonitrile, methacrylonitrile, N-substituted cyclic imide and maleic anhydride.
7. The lithographic printing plate precursor according to claim 1, characterized in that: the average molecular weight of the polymer containing carbon in the main chain is 5000-100000.
8. The lithographic printing plate precursor according to claim 1, characterized in that: the low molecular weight hydrophilic organic compound used as the development accelerator is polyhydric alcohol and ether or ester derivatives thereof, organic amine and salts thereof, organic sulfonic acid and salts thereof; the high molecular weight hydrophilic polymer used as the development accelerator is polyethylene glycol, gum arabic, starch, cellulose, dextrin, polysaccharide, and a homopolymer or copolymer containing a carboxyl group, a sulfonic acid group, a phosphonic acid group, an amide group, and a vinyl pyrrolidone monomer.
9. A plate making method of a photosensitive negative-working planographic printing plate, characterized by comprising the steps of:
(1) Pattern-wise exposing any one of the light-sensitive negative-working lithographic printing plate precursors of claims 1-8 to form exposed and unexposed regions;
(2) Removing the unexposed areas of the exposed printing plate precursor by a developing process to obtain the desired lithographic printing plate, characterized in that: the developing step is any one of the following steps: (i) on-press development: performing development on the press using a fountain solution and/or lithographic printing ink; (ii) off-press development: the development is carried out in a plate processor outside the printing press using a developer solution.
10. A plate-making process according to claim 9, wherein: the developing solution for off-machine development comprises carbonate and/or bicarbonate, the mass fraction of the carbonate and/or bicarbonate in the developing solution is 1-20%, and the pH value of the developing solution is 6-11.
11. A plate-making process according to claim 10, wherein: the carbonate in the developing solution is alkali metal carbonate; the bicarbonate in the developing solution is alkali metal bicarbonate.
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Denomination of invention: A photosensitive negative type Planographic printing plate precursor and a Planographic printing plate making method using the precursor

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