CN101192004B - Chemical processing-free negative graph photosensitive composition suitable for UV-CTP and planographic printing plate manufactured therefor and planographic printing plate manufacture method - Google Patents
Chemical processing-free negative graph photosensitive composition suitable for UV-CTP and planographic printing plate manufactured therefor and planographic printing plate manufacture method Download PDFInfo
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Abstract
本发明公开了一种适合于UV-CTP的免化学处理阴图感光组成物和用其制作的平印版及平印版制作方法，其主要包含：(1)一种-(X)-(Y)-(Z)-结构的不饱和水溶性聚合物，其特征在于，X代表含有磺酸基团的共聚单元，Y代表含有两个不饱和双键的支链的羧酸共聚单元，Z代表含有一个不饱和双键支链的丙烯酸酯共聚单元，和(2)一种可光聚合的预聚体、和(3)一种多官能团单体，和(4)一种或一种以上的光聚合引发剂，和(5)一种或一种以上的染料或颜料。本发明适合于UV-CTP制版机的平印版，本发明平印版感光度高、网点还愿性好，在紫外线光源曝光后可直接用自来水冲洗或不经任何冲洗加工步骤即可上机印刷，并可得到高的耐印力，尤其适合UV-CTP制版机。
The invention discloses a chemical-free negative photosensitive composition suitable for UV-CTP, a lithographic plate made by using it, and a lithographic plate manufacturing method, which mainly include: (1) a -(X)-( The unsaturated water-soluble polymer of Y)-(Z)-structure is characterized in that X represents a copolymerization unit containing sulfonic acid groups, Y represents a branched carboxylic acid copolymerization unit containing two unsaturated double bonds, and Z Represents an acrylate copolymerized unit containing an unsaturated double bond branch, and (2) a photopolymerizable prepolymer, and (3) a multifunctional monomer, and (4) one or more A photopolymerization initiator, and (5) one or more dyes or pigments. The present invention is suitable for the lithographic printing plate of UV-CTP plate making machine. The lithographic printing plate of the present invention has high sensitivity and good dot resolution, and can be directly washed with tap water or printed on the machine without any washing processing steps after being exposed to the ultraviolet light source. , and can get high printing force, especially suitable for UV-CTP plate making machine.
Description
Technical field
The present invention relates to the chemical processing-free negative graph photosensitive composition of a kind of UV-CTP of being suitable for and with the flat stamping version and the planographic printing plate manufacture method of its making.
Background technology
The preparation process of flat stamping version is known by the people in the industry in printing industry.The plate-making process of flat stamping version needed for two steps finished at least, the one, with the forme that has been coated with photosensitive composition by frisket (as, positive type and negative-type frisket) under specific light source, expose, form an optical image latent image therefrom; The 2nd, the forme after the top exposure is carried out a so-called follow-up development step, by this process, remove excess coating.The pre-coating photosensitive lithographic plate is to be the flaky material of support with aluminium or polyester, and can make by above-mentioned two steps and have oleophylic and hydrophilic surface simultaneously, is suitable for lithography.Usually, in a negative-type system, the exposure position becomes the insoluble or indissoluble of developer solution, thereby can in development step the coating at the unexposed position of forme be removed owing to the polymerization or crosslinked the changing of coating.Otherwise in a positive type system, development step is that the expose material at position of forme is removed.Development step generally includes with developer rinsing and washing, develops in a processing unit that contains developer usually.The used developer of positive-type flat stamping version is highly basic normally, also contains organic solvent in the negative type developer solution usually except that highly basic, as phenmethylol etc.Certainly, also useful heating means of the development of optical image or alternate manner are finished.
The shortcoming of above-mentioned two kinds (promptly wet and heat) developing processs be consuming time, cost is very high.And when adopting volatile organic matter or highly basic as developer, the processing of these waste liquids will bring environmental problem.
Along with the development of printing industry and the raising of people's living standard, countries in the world are more and more higher to environmental protection requirement, so just need a kind of forme that before printing, does not need chemical treatment or do not need any processing, this not only can help environmental protection, and this setup time that also will help the space of reducing printing cost, reducing pressroom and reduce presswork.
The structure of the positive type forme that need not handle before the printing after imaging is disclosed (as seeing U.S. Patent No. 5,102,771; 5,225,316 and 5,314,785).These patent disclosures based on the forme and the light acid generation system of the light sensitive layer that contains acrylate or methacrylate polymers.When image is exposed to optical radiation following time, the polymer unwinds in the rayed zone forms water wettability, and keeps ink affinity at the polymkeric substance that is not having light-struck zone.
The pre-coating photosensitive negative-type lithographic plate that need not handle before the printing after imaging also is that this field is known. between imaging and printing, do not need the kind of treatment step forme in U.S. Patent No. 3,231,378; 3,285,745; With 3,409, open in 487. these formes contain a kind of phenolics that comprises, the photosensitive composition of ethylene oxide polymer and light sensitizer. when it is exposed to actinic radiation following time, make phenolics generation oxidation, thereby having increased ink affinity. the shortcoming of these formes is that their ink affinities in printing process easily reduce, so that need the balance between strict China ink/water of controlling on the printing machine could guarantee normal printing, sometimes also can make forme become and can not operate. U.S. Patent No. 3,793,033 discloses added people's hydroxy ethyl cellulose ester in constituent. and the forme of acquisition can not become blind version, and (lithographic plate is not subjected to China ink when promptly printing, image impairment), and only needing to carry out less control to the China ink/water balance on the printing machine. a tangible adverse condition of this composition is to obtain suitable printing machine printing with the phenolics that need solidify. so just need on the printing plate precursor that makes, form a two-layer system, if promptly should add one deck sensitizer layer again containing on the phenolics layer. will decompose when phenolics is in curing so not being coated with the sensitizer layer after the curing.
The another kind of negative-type forme that need not handle at imaging and pressroom is those formes based on the multilayer photographic layer.Usually, as in U.S. Patent No. 4,600,679 and 4,104,072 and European Patent Publication No No.450, described in 199, these structures have a hydrophilic photographic layer at the most close version base, and an extra play that is used for photo-hardening is connected with ground floor.These structures are the hydrophilic layer of the negative-type photosensitive composition on basis as the most close version base in order to the aromatics diazo-compounds usually.A shortcoming of these formes is its trend that scumming (being China ink on the background position) is arranged and pollute printing machine.This shortcoming need be cleaned forme with suitable clean-out system (being fountain solution) earlier before printing. and therefore, the adding of diazo-compounds and resin is harmful to for the forme that is used for " non-processor " version.Disclosed forme among the PCT application number No.93-05446 does not wherein have the diazonium composition in the hydrophilic layer, therefore eliminated because the residual caused printing machine pollution problem of unreacted diazo substance.Described version comprises version/version base, the sensitization polymerization hydrophilic layer of the most approaching version base and one the second photopolymer hydrophobic layer that separates near the version base.The sensitization hydrophilic layer is based on the polymerizable material of diazonium-containing compound not.The functionality of version loses water-soluble under actinic radiation by two layer exposures and sclerosis obtains.This edition only needs a printing machine that China ink and fountain solution are housed with the good printed matter of acquisition after exposure, and do not need to carry out before printing the prewashing version.Because this structure has the outer hydrophobic layer, so just can not obtain performance of ink with edition identical the water of routine if before printing, do not handle the hydrophobic substance of removing background parts.
Summary of the invention
The object of the present invention is to provide a kind of light sensitivity height, redeeming a vow to a god property of site good, can be directly after the ultraviolet light source exposure with the tap water flushing or without any washing processing step promptly be available on the machine printing, also can obtain the chemical processing-free negative graph photosensitive composition that is suitable for UV-CTP of high pressrun and with the flat stamping version and the planographic printing plate manufacture method of its making.
Purpose of the present invention can realize by following measure:
The chemical processing-free negative graph photosensitive composition that the present invention is suitable for UV-CTP mainly comprises following six kinds of components: (1) a kind of-(X)-(Y)-(Z)-and the unsaturated water-soluble polymers of structure, (2) a kind of performed polymer of photopolymerization and (3) a kind of polyfunctional monomer, (4) one or more Photoepolymerizationinitiater initiater, (5) one or more solvent of one or more dyestuff or pigment and (6); Wherein, the X representative contains the copolymerization units of sulfonic acid group, and the Y representative contains the carboxyl acid copolymer unit of the side chain of two unsaturated double-bonds, and the Z representative contains the acrylic ester copolymer unit of a unsaturated double-bond side chain.
The present invention is suitable for that X is selected from vinyl sulfonic acid, styrene sulfonic acid, 2-hydroxyl-3-allyloxy-1-propyl sulfonic acid, allyloxy benzene sulfonic acid, 2-acrylamido-2-methyl-propyl sulfonic acid, isoprene sulfonic acid in the chemical processing-free negative graph photosensitive composition of UV-CTP.X accounts for 10%～30% mol ratio of multipolymer.Y is the acrylic or methacrylic acid copolymerization units that contains the side chain of two unsaturated double-bonds.Perhaps, Y is the acrylic or methacrylic acid copolymerization units that contains the GMA grafting of a unsaturated double-bond replacement.Y accounts for 20%～40% mol ratio of multipolymer.Z is acrylate or the methacrylic acid copolymerization units that contains a unsaturated double-bond substituted radical.Z accounts for 30%～50% mol ratio of multipolymer.-(X)-(Y)-(Z)-the unsaturated water-soluble polymers of structure in, the unsaturated double-bond sum accounts for the 60-80% mol ratio of polymkeric substance.The performed polymer of photopolymerization is a kind of polyurethane acroleic acid performed polymer.Photopolymerizable monomer is a polyfunctional monomer.Photoepolymerizationinitiater initiater is selected from the triaizine compounds that halogen replaces.The chemical processing-free negative graph photosensitive composition that is suitable for UV-CTP also contains any one or more combination conduct interpolation component in phenolics, acryl resin, the urethane resin.
The present invention is suitable for the flat stamping version that the chemical processing-free negative graph photosensitive composition of UV-CTP is made, it comprises: (1) aluminum substrate support, (2) on the aluminum substrate support contain above-mentioned-(X)-(Y)-(Z)-hydrophilic layer and (3) and the chemical processing-free negative graph photosensitive composition coating layer of hydrophilic layer of the unsaturated water-soluble polymers of structure at the above-mentioned UV-CTP of being suitable for aluminum substrate the same side and on hydrophilic layer.
Flat stamping version of the present invention, the support of this flat stamping version are through electrolyzing and coarsening and anodic oxidation and carry out the aluminum substrate that sealing of hole is handled that its center line average boldness is at 0.4-0.6um.The coating dry weight of hydrophilicity-imparting treatment is 5～50mg/dm
2
The method for making of flat stamping version of the present invention is being coated with the above-mentioned chemical processing-free negative graph photosensitive composition that is suitable for UV-CTP through electrolyzing and coarsening and anodic oxidation and on the aluminum substrate after carrying out the sealing of hole processing.
The method for making of flat stamping version among the present invention, through before electrolyzing and coarsening and anodic oxidation and carrying out the above-mentioned chemical processing-free negative graph photosensitive composition that is suitable for UV-CTP of coating on the aluminum substrate after sealing of hole is handled, aluminum substrate is carried out hydrophilicity-imparting treatment with the unsaturated water-soluble polymers of the present invention-(X)-(Y)-(Z)-structure.This flat stamping version is suitable for using the plate-making of UV-CTP platemaking machine.This flat stamping version can not used developing liquid developing and uses the tap water flushing after using UV-CTP platemaking machine scan exposure, promptly obtains printable flat stamping version.This flat stamping version directly can be lockd up press printing without any processing after using UV-CTP platemaking machine scan exposure.
The present invention is owing to adopt component and method, make it to have plurality of advantages, concrete comparing data is as follows: (advantage summary, please put inferior place in order) light sensitivity height, redeeming a vow to a god property of site be good, can be directly after with the ultraviolet light source exposure with the tap water flushing or without the printing that promptly is available on the machine of any washing processing step.Forme picture and text part lipophilicity is good, and blank parts does not go up dirty, and can obtain high pressrun, especially is fit to the UV-CTP platemaking machine.
Its performance is listed in the table one of back (embodiment refers to the embodiment of embodiment second portion in the table).
Table one
Description of drawings
Accompanying drawing is the cross section structure synoptic diagram of flat stamping version among the present invention;
Embodiment
The present invention does with detailed description below in conjunction with drawings and Examples:
Embodiment first
The chemical processing-free negative graph photosensitive composition that the present invention is suitable for UV-CTP mainly comprises following six kinds of components: (1) a kind of-(X)-(Y)-(Z)-and the unsaturated water-soluble polymers of structure, (2) a kind of performed polymer of photopolymerization and (3) a kind of polyfunctional monomer, (4) one or more Photoepolymerizationinitiater initiater, (5) one or more solvent of one or more dyestuff or pigment and (6); Wherein, the X representative contains the copolymerization units of sulfonic acid group, and the Y representative contains the carboxyl acid copolymer unit of the side chain of two unsaturated double-bonds, and the Z representative contains the acrylic ester copolymer unit of a unsaturated double-bond side chain.
The present invention is suitable for that X is selected from vinyl sulfonic acid, styrene sulfonic acid, 2-hydroxyl-3-allyloxy-1-propyl sulfonic acid, allyloxy benzene sulfonic acid, 2-acrylamido-2-methyl-propyl sulfonic acid, isoprene sulfonic acid in the chemical processing-free negative graph photosensitive composition of UV-CTP.X accounts for 10% mol ratio of multipolymer.Y is the acrylic or methacrylic acid copolymerization units that contains the side chain of two unsaturated double-bonds.Perhaps, Y is the acrylic or methacrylic acid copolymerization units that contains the GMA grafting of a unsaturated double-bond replacement.Y accounts for 20% mol ratio of multipolymer.Z is acrylate or the methacrylic acid copolymerization units that contains a unsaturated double-bond substituted radical.Z accounts for 30% mol ratio of multipolymer.-(X)-(Y)-(Z)-the unsaturated water-soluble polymers of structure in, the unsaturated double-bond sum accounts for 60% mol ratio of polymkeric substance.The performed polymer of photopolymerization is a kind of polyurethane acroleic acid performed polymer.Photopolymerizable monomer is a polyfunctional monomer.Photoepolymerizationinitiater initiater is selected from the triaizine compounds that halogen replaces.The chemical processing-free negative graph photosensitive composition that is suitable for UV-CTP also contains any one or more combination conduct interpolation component in phenolics, acryl resin, the urethane resin.
The present invention is suitable for the flat stamping version that the chemical processing-free negative graph photosensitive composition of UV-CTP is made, it comprises: (1) aluminum substrate support (label 3, other are same), (2) on the aluminum substrate support contain above-mentioned-(X)-(Y)-(Z)-hydrophilic layer of the unsaturated water-soluble polymers of structure (label 2 other with) and (3) and hydrophilic layer be at the chemical processing-free negative graph photosensitive composition coating layer of the above-mentioned UV-CTP of being suitable for aluminum substrate the same side and on hydrophilic layer (label 3 other).
Flat stamping version of the present invention, the support of this flat stamping version are through electrolyzing and coarsening and anodic oxidation and carry out the aluminum substrate that sealing of hole is handled that its center line average boldness is at 0.4um.The coating dry weight of hydrophilicity-imparting treatment is 5mg/dm
2
The method for making of flat stamping version of the present invention is being coated with the above-mentioned chemical processing-free negative graph photosensitive composition that is suitable for UV-CTP through electrolyzing and coarsening and anodic oxidation and on the aluminum substrate after carrying out the sealing of hole processing.
The method for making of flat stamping version among the present invention, through before electrolyzing and coarsening and anodic oxidation and carrying out the above-mentioned chemical processing-free negative graph photosensitive composition that is suitable for UV-CTP of coating on the aluminum substrate after sealing of hole is handled, aluminum substrate is carried out hydrophilicity-imparting treatment with the unsaturated water-soluble polymers of the present invention-(X)-(Y)-(Z)-structure.This flat stamping version is suitable for using the plate-making of UV-CTP platemaking machine.This flat stamping version can not used developing liquid developing and uses the tap water flushing after using UV-CTP platemaking machine scan exposure, promptly obtains printable flat stamping version.This flat stamping version directly can be lockd up press printing without any processing after using UV-CTP platemaking machine scan exposure.
The chemical processing-free negative graph photosensitive composition that the present invention is suitable for UV-CTP mainly comprises following six kinds of components: (1) a kind of-(X)-(Y)-(Z)-and the unsaturated water-soluble polymers of structure, (2) a kind of performed polymer of photopolymerization and (3) a kind of polyfunctional monomer, (4) one or more Photoepolymerizationinitiater initiater, (5) one or more solvent of one or more dyestuff or pigment and (6); Wherein, the X representative contains the copolymerization units of sulfonic acid group, and the Y representative contains the carboxyl acid copolymer unit of the side chain of two unsaturated double-bonds, and the Z representative contains the acrylic ester copolymer unit of a unsaturated double-bond side chain.
The present invention is suitable for that X is selected from vinyl sulfonic acid in the chemical processing-free negative graph photosensitive composition of UV-CTP, styrene sulfonic acid, 2-hydroxyl-3-allyloxy-1-propyl sulfonic acid, the allyloxy benzene sulfonic acid, 2-acrylamido-2-methyl-propyl sulfonic acid, the 15% mol ratio .Y that isoprene sulfonic acid .X accounts for multipolymer is the acrylic or methacrylic acid copolymerization units that contains the side chain of two unsaturated double-bonds. perhaps, Y is that the 25% mol ratio .Z that the acrylic or methacrylic acid copolymerization units .Y that contains the GMA grafting that unsaturated double-bond replaces accounts for multipolymer contains in the unsaturated water-soluble polymers of the acrylate of a unsaturated double-bond substituted radical or 35% mol ratio .-(X)-(Y)-(Z)-structure that methacrylic acid copolymerization units .Z accounts for multipolymer, and the unsaturated double-bond sum accounts for 65% mol ratio of polymkeric substance. and the performed polymer of photopolymerization is a kind of polyurethane acroleic acid performed polymer. and photopolymerizable monomer is a polyfunctional monomer. and Photoepolymerizationinitiater initiater is selected from the triaizine compounds that halogen replaces. and the chemical processing-free negative graph photosensitive composition that is suitable for UV-CTP also contains phenolics, acryl resin, any one or more combination is as adding component in the urethane resin.
The present invention is suitable for the flat stamping version that the chemical processing-free negative graph photosensitive composition of UV-CTP is made, it comprises: (1) aluminum substrate support, (2) on the aluminum substrate support contain above-mentioned-(X)-(Y)-(Z)-hydrophilic layer and (3) and the chemical processing-free negative graph photosensitive composition coating layer of hydrophilic layer of the unsaturated water-soluble polymers of structure at the above-mentioned UV-CTP of being suitable for aluminum substrate the same side and on hydrophilic layer.
Flat stamping version of the present invention, the support of this flat stamping version are through electrolyzing and coarsening and anodic oxidation and carry out the aluminum substrate that sealing of hole is handled that its center line average boldness is at 0.45um.The coating dry weight of hydrophilicity-imparting treatment is 15mg/dm
2
The method for making of flat stamping version of the present invention is being coated with the above-mentioned chemical processing-free negative graph photosensitive composition that is suitable for UV-CTP through electrolyzing and coarsening and anodic oxidation and on the aluminum substrate after carrying out the sealing of hole processing.
The method for making of flat stamping version among the present invention, through before electrolyzing and coarsening and anodic oxidation and carrying out the above-mentioned chemical processing-free negative graph photosensitive composition that is suitable for UV-CTP of coating on the aluminum substrate after sealing of hole is handled, aluminum substrate is carried out hydrophilicity-imparting treatment with the unsaturated water-soluble polymers of the present invention-(X)-(Y)-(Z)-structure.This flat stamping version is suitable for using the plate-making of UV-CTP platemaking machine.This flat stamping version can not used developing liquid developing and uses the tap water flushing after using UV-CTP platemaking machine scan exposure, promptly obtains printable flat stamping version.This flat stamping version directly can be lockd up press printing without any processing after using UV-CTP platemaking machine scan exposure.
The chemical processing-free negative graph photosensitive composition that the present invention is suitable for UV-CTP mainly comprises following six kinds of components: (1) a kind of-(X)-(Y)-(Z)-and the unsaturated water-soluble polymers of structure, (2) a kind of performed polymer of photopolymerization and (3) a kind of polyfunctional monomer, (4) one or more Photoepolymerizationinitiater initiater, (5) one or more solvent of one or more dyestuff or pigment and (6); Wherein, the X representative contains the copolymerization units of sulfonic acid group, and the Y representative contains the carboxyl acid copolymer unit of the side chain of two unsaturated double-bonds, and the Z representative contains the acrylic ester copolymer unit of a unsaturated double-bond side chain.
The present invention is suitable for that X is selected from vinyl sulfonic acid, styrene sulfonic acid, 2-hydroxyl-3-allyloxy-1-propyl sulfonic acid, allyloxy benzene sulfonic acid, 2-acrylamido-2-methyl-propyl sulfonic acid, isoprene sulfonic acid in the chemical processing-free negative graph photosensitive composition of UV-CTP.X accounts for 20% mol ratio of multipolymer.Y is the acrylic or methacrylic acid copolymerization units that contains the side chain of two unsaturated double-bonds.Perhaps, Y is the acrylic or methacrylic acid copolymerization units that contains the GMA grafting of a unsaturated double-bond replacement.Y accounts for 30% mol ratio of multipolymer.Z is acrylate or the methacrylic acid copolymerization units that contains a unsaturated double-bond substituted radical.Z accounts for 40% mol ratio of multipolymer.-(X)-(Y)-(Z)-the unsaturated water-soluble polymers of structure in, the unsaturated double-bond sum accounts for 70% mol ratio of polymkeric substance.The performed polymer of photopolymerization is a kind of polyurethane acroleic acid performed polymer.Photopolymerizable monomer is a polyfunctional monomer.Photoepolymerizationinitiater initiater is selected from the triaizine compounds that halogen replaces.The chemical processing-free negative graph photosensitive composition that is suitable for UV-CTP also contains any one or more combination conduct interpolation component in phenolics, acryl resin, the urethane resin.
The present invention is suitable for the flat stamping version that the chemical processing-free negative graph photosensitive composition of UV-CTP is made, it comprises: (1) aluminum substrate support, (2) on the aluminum substrate support contain above-mentioned-(X)-(Y)-(Z)-hydrophilic layer and (3) and the chemical processing-free negative graph photosensitive composition coating layer of hydrophilic layer of the unsaturated water-soluble polymers of structure at the above-mentioned UV-CTP of being suitable for aluminum substrate the same side and on hydrophilic layer.
Flat stamping version of the present invention, the support of this flat stamping version are through electrolyzing and coarsening and anodic oxidation and carry out the aluminum substrate that sealing of hole is handled that its center line average boldness is at 0.5um.The coating dry weight of hydrophilicity-imparting treatment is 30mg/dm
2
The method for making of flat stamping version of the present invention is being coated with the above-mentioned chemical processing-free negative graph photosensitive composition that is suitable for UV-CTP through electrolyzing and coarsening and anodic oxidation and on the aluminum substrate after carrying out the sealing of hole processing.
The method for making of flat stamping version among the present invention, through before electrolyzing and coarsening and anodic oxidation and carrying out the above-mentioned chemical processing-free negative graph photosensitive composition that is suitable for UV-CTP of coating on the aluminum substrate after sealing of hole is handled, aluminum substrate is carried out hydrophilicity-imparting treatment with the unsaturated water-soluble polymers of the present invention-(X)-(Y)-(Z)-structure.This flat stamping version is suitable for using the plate-making of UV-CTP platemaking machine.This flat stamping version can not used developing liquid developing and uses the tap water flushing after using UV-CTP platemaking machine scan exposure, promptly obtains printable flat stamping version.This flat stamping version directly can be lockd up press printing without any processing after using UV-CTP platemaking machine scan exposure.
Embodiment 4
The chemical processing-free negative graph photosensitive composition that the present invention is suitable for UV-CTP mainly comprises following six kinds of components: (1) a kind of-(X)-(Y)-(Z)-and the unsaturated water-soluble polymers of structure, (2) a kind of performed polymer of photopolymerization and (3) a kind of polyfunctional monomer, (4) one or more Photoepolymerizationinitiater initiater, (5) one or more solvent of one or more dyestuff or pigment and (6); Wherein, the X representative contains the copolymerization units of sulfonic acid group, and the Y representative contains the carboxyl acid copolymer unit of the side chain of two unsaturated double-bonds, and the Z representative contains the acrylic ester copolymer unit of a unsaturated double-bond side chain.
The present invention is suitable for that X is selected from vinyl sulfonic acid, styrene sulfonic acid, 2-hydroxyl-3-allyloxy-1-propyl sulfonic acid, allyloxy benzene sulfonic acid, 2-acrylamido-2-methyl-propyl sulfonic acid, isoprene sulfonic acid in the chemical processing-free negative graph photosensitive composition of UV-CTP.X accounts for 25% mol ratio of multipolymer.Y is the acrylic or methacrylic acid copolymerization units that contains the side chain of two unsaturated double-bonds.Perhaps, Y is the acrylic or methacrylic acid copolymerization units that contains the GMA grafting of a unsaturated double-bond replacement.Y accounts for 35% mol ratio of multipolymer.Z is acrylate or the methacrylic acid copolymerization units that contains a unsaturated double-bond substituted radical.Z accounts for 45% mol ratio of multipolymer.-(X)-(Y)-(Z)-the unsaturated water-soluble polymers of structure in, the unsaturated double-bond sum accounts for 75% mol ratio of polymkeric substance.The performed polymer of photopolymerization is a kind of polyurethane acroleic acid performed polymer.Photopolymerizable monomer is a polyfunctional monomer.Photoepolymerizationinitiater initiater is selected from the triaizine compounds that halogen replaces.The chemical processing-free negative graph photosensitive composition that is suitable for UV-CTP also contains any one or more combination conduct interpolation component in phenolics, acryl resin, the urethane resin.
The present invention is suitable for the flat stamping version that the chemical processing-free negative graph photosensitive composition of UV-CTP is made, it comprises: (1) aluminum substrate support, (2) on the aluminum substrate support contain above-mentioned-(X)-(Y)-(Z)-hydrophilic layer and (3) and the chemical processing-free negative graph photosensitive composition coating layer of hydrophilic layer of the unsaturated water-soluble polymers of structure at the above-mentioned UV-CTP of being suitable for aluminum substrate the same side and on hydrophilic layer.
Flat stamping version of the present invention, the support of this flat stamping version are through electrolyzing and coarsening and anodic oxidation and carry out the aluminum substrate that sealing of hole is handled that its center line average boldness is at 0.55um.The coating dry weight of hydrophilicity-imparting treatment is 40mg/dm
2
The method for making of flat stamping version of the present invention is being coated with the above-mentioned chemical processing-free negative graph photosensitive composition that is suitable for UV-CTP through electrolyzing and coarsening and anodic oxidation and on the aluminum substrate after carrying out the sealing of hole processing.
The method for making of flat stamping version among the present invention, through before electrolyzing and coarsening and anodic oxidation and carrying out the above-mentioned chemical processing-free negative graph photosensitive composition that is suitable for UV-CTP of coating on the aluminum substrate after sealing of hole is handled, unsaturated water-soluble polymers with the present invention-(X)-(Y)-(Z)-structure carries out hydrophilicity-imparting treatment to aluminum substrate. and this flat stamping version is suitable for using the plate-making of UV-CTP platemaking machine. and this flat stamping version is after using UV-CTP platemaking machine scan exposure, can not use developing liquid developing and use the tap water flushing, promptly obtaining printable flat stamping version. this flat stamping version directly can be lockd up press printing without any processing after using UV-CTP platemaking machine scan exposure.
Embodiment 5
The chemical processing-free negative graph photosensitive composition that the present invention is suitable for UV-CTP mainly comprises following six kinds of components: (1) a kind of-(X)-(Y)-(Z)-and the unsaturated water-soluble polymers of structure, (2) a kind of performed polymer of photopolymerization and (3) a kind of polyfunctional monomer, (4) one or more Photoepolymerizationinitiater initiater, (5) one or more solvent of one or more dyestuff or pigment and (6); Wherein, the X representative contains the copolymerization units of sulfonic acid group, and the Y representative contains the carboxyl acid copolymer unit of the side chain of two unsaturated double-bonds, and the Z representative contains the acrylic ester copolymer unit of a unsaturated double-bond side chain.
The present invention is suitable for that X is selected from vinyl sulfonic acid, styrene sulfonic acid, 2-hydroxyl-3-allyloxy-1-propyl sulfonic acid, allyloxy benzene sulfonic acid, 2-acrylamido-2-methyl-propyl sulfonic acid, isoprene sulfonic acid in the chemical processing-free negative graph photosensitive composition of UV-CTP.X accounts for 30% mol ratio of multipolymer.Y is the acrylic or methacrylic acid copolymerization units that contains the side chain of two unsaturated double-bonds.Perhaps, Y is the acrylic or methacrylic acid copolymerization units that contains the GMA grafting of a unsaturated double-bond replacement.Y accounts for 40% mol ratio of multipolymer.Z is acrylate or the methacrylic acid copolymerization units that contains a unsaturated double-bond substituted radical.Z accounts for 50% mol ratio of multipolymer.-(X)-(Y)-(Z)-the unsaturated water-soluble polymers of structure in, the unsaturated double-bond sum accounts for 80% mol ratio of polymkeric substance.The performed polymer of photopolymerization is a kind of polyurethane acroleic acid performed polymer.Photopolymerizable monomer is a polyfunctional monomer.Photoepolymerizationinitiater initiater is selected from the triaizine compounds that halogen replaces.The chemical processing-free negative graph photosensitive composition that is suitable for UV-CTP also contains any one or more combination conduct interpolation component in phenolics, acryl resin, the urethane resin.
The present invention is suitable for the flat stamping version that the chemical processing-free negative graph photosensitive composition of UV-CTP is made, it comprises: (1) aluminum substrate support, (2) on the aluminum substrate support contain above-mentioned-(X)-(Y)-(Z)-hydrophilic layer and (3) and the chemical processing-free negative graph photosensitive composition coating layer of hydrophilic layer of the unsaturated water-soluble polymers of structure at the above-mentioned UV-CTP of being suitable for aluminum substrate the same side and on hydrophilic layer.
Flat stamping version of the present invention, the support of this flat stamping version are through electrolyzing and coarsening and anodic oxidation and carry out the aluminum substrate that sealing of hole is handled that its center line average boldness is at 0.6um.The coating dry weight of hydrophilicity-imparting treatment is 50mg/dm
2
The method for making of flat stamping version of the present invention is being coated with the above-mentioned chemical processing-free negative graph photosensitive composition that is suitable for UV-CTP through electrolyzing and coarsening and anodic oxidation and on the aluminum substrate after carrying out the sealing of hole processing.
The method for making of flat stamping version among the present invention, through before electrolyzing and coarsening and anodic oxidation and carrying out the above-mentioned chemical processing-free negative graph photosensitive composition that is suitable for UV-CTP of coating on the aluminum substrate after sealing of hole is handled, aluminum substrate is carried out hydrophilicity-imparting treatment with the unsaturated water-soluble polymers of the present invention-(X)-(Y)-(Z)-structure.This flat stamping version is suitable for using the plate-making of UV-CTP platemaking machine.This flat stamping version can not used developing liquid developing and uses the tap water flushing after using UV-CTP platemaking machine scan exposure, promptly obtains printable flat stamping version.This flat stamping version directly can be lockd up press printing without any processing after using UV-CTP platemaking machine scan exposure.
Embodiment 6
The chemical processing-free negative graph photosensitive composition that the present invention is suitable for UV-CTP mainly comprises following six kinds of components: (1) a kind of-(X)-(Y)-(Z)-and the unsaturated water-soluble polymers of structure, (2) a kind of performed polymer of photopolymerization and (3) a kind of polyfunctional monomer, (4) one or more Photoepolymerizationinitiater initiater, (5) one or more solvent of one or more dyestuff or pigment and (6); Wherein, the X representative contains the copolymerization units of sulfonic acid group, and the Y representative contains the carboxyl acid copolymer unit of the side chain of two unsaturated double-bonds, and the Z representative contains the acrylic ester copolymer unit of a unsaturated double-bond side chain.
The present invention is suitable for that X is selected from vinyl sulfonic acid, styrene sulfonic acid, 2-hydroxyl-3-allyloxy-1-propyl sulfonic acid, allyloxy benzene sulfonic acid, 2-acrylamido-2-methyl-propyl sulfonic acid, isoprene sulfonic acid in the chemical processing-free negative graph photosensitive composition of UV-CTP.X accounts for 10%～30% mol ratio of multipolymer.Y is the acrylic or methacrylic acid copolymerization units that contains the side chain of two unsaturated double-bonds.Perhaps, Y is the acrylic or methacrylic acid copolymerization units that contains the GMA grafting of a unsaturated double-bond replacement.Y accounts for 20%～40% mol ratio of multipolymer.Z is acrylate or the methacrylic acid copolymerization units that contains a unsaturated double-bond substituted radical.Z accounts for 30%～50% mol ratio of multipolymer.-(X)-(Y)-(Z)-the unsaturated water-soluble polymers of structure in, the unsaturated double-bond sum accounts for the 60-80% mol ratio of polymkeric substance.The performed polymer of photopolymerization is a kind of polyurethane acroleic acid performed polymer.Photopolymerizable monomer is a polyfunctional monomer.Photoepolymerizationinitiater initiater is selected from the triaizine compounds that halogen replaces.The chemical processing-free negative graph photosensitive composition that is suitable for UV-CTP also contains any one or more combination conduct interpolation component in phenolics, acryl resin, the urethane resin.
The present invention is suitable for the flat stamping version that the chemical processing-free negative graph photosensitive composition of UV-CTP is made, it comprises: (1) aluminum substrate support, (2) on the aluminum substrate support contain above-mentioned-(X)-(Y)-(Z)-hydrophilic layer and (3) and the chemical processing-free negative graph photosensitive composition coating layer of hydrophilic layer of the unsaturated water-soluble polymers of structure at the above-mentioned UV-CTP of being suitable for aluminum substrate the same side and on hydrophilic layer.
Flat stamping version of the present invention, the support of this flat stamping version are through electrolyzing and coarsening and anodic oxidation and carry out the aluminum substrate that sealing of hole is handled that its center line average boldness is at 0.4-0.6um.The coating dry weight of hydrophilicity-imparting treatment is 5～50mg/dm
2
The method for making of flat stamping version of the present invention is being coated with the above-mentioned chemical processing-free negative graph photosensitive composition that is suitable for UV-CTP through electrolyzing and coarsening and anodic oxidation and on the aluminum substrate after carrying out the sealing of hole processing.
The method for making of flat stamping version among the present invention, through before electrolyzing and coarsening and anodic oxidation and carrying out the above-mentioned chemical processing-free negative graph photosensitive composition that is suitable for UV-CTP of coating on the aluminum substrate after sealing of hole is handled, aluminum substrate is carried out hydrophilicity-imparting treatment with the unsaturated water-soluble polymers of the present invention-(X)-(Y)-(Z)-structure.This flat stamping version is suitable for using the plate-making of UV-CTP platemaking machine.This flat stamping version can not used developing liquid developing and uses the tap water flushing after using UV-CTP platemaking machine scan exposure, promptly obtains printable flat stamping version.This flat stamping version directly can be lockd up press printing without any processing after using UV-CTP platemaking machine scan exposure.Above-mentioned as required each parameter can be got the arbitrary value of its value range.
The embodiment second portion
Flat stamping version light sensitivity height of the present invention, redeeming a vow to a god property of site are good, can be directly after with the ultraviolet light source exposure with the tap water flushing or without the printing that promptly is available on the machine of any washing processing step.Forme picture and text part lipophilicity is good, and blank parts does not go up dirty, and can obtain high pressrun, especially is fit to the plate-making of UV-CTP platemaking machine.Flat stamping version of the present invention does not contain diazo salt, and has single photographic layer structure.Flat stamping version light sensitivity height of the present invention, redeeming a vow to a god property of site are good, can be directly after the ultraviolet light source exposure with the tap water flushing or without the printing that promptly is available on the machine of any washing processing step, and can obtain high pressrun, especially suitable UV-CTP platemaking machine.Purpose of the present invention can realize by following measure:
The chemical processing-free negative graph photosensitive composition that the present invention is suitable for UV-CTP (is called for short photosensitive composition, other with) comprise: (1) a kind of-(X)-(Y)-(Z)-the unsaturated water-soluble polymers of structure, it is characterized in that, the X representative contains the copolymerization units of sulfonic acid group, the Y representative contains the carboxyl acid copolymer unit of two unsaturated double-bond side chains, the Z representative contains the acrylic ester copolymer unit of a unsaturated double-bond side chain, (2) a kind of performed polymer of photopolymerization, (3) a kind of polyfunctional monomer, (4) one or more dyestuff or pigment of one or more Photoepolymerizationinitiater initiater and (5).
Flat stamping version of the present invention is by doing support through electrolyzing and coarsening and the aluminum substrate after anodic oxidation and sealing of hole processing, and being coated with photosensitive composition of the present invention thereon and obtaining. the center line average boldness of this support is at 0.4-0.6um, before coating photosensitive composition of the present invention, the version base is carried out hydrophilicity-imparting treatment with the solution of the water soluble resin of the present invention-(X)-(Y)-(Z)-structure.
In the photosensitive composition of the present invention-(X)-(Y)-(Z)-polymkeric substance of structure is a kind of water-soluble polymers that contains unsaturated double-bond.Wherein, the X representative contains the copolymerization units of sulfonic acid group, and the Y representative contains the carboxyl acid copolymer unit of two unsaturated double-bond side chains, and the Z representative contains the acrylic ester copolymer unit of a unsaturated double-bond side chain.
As the copolymerization units of X representative, can so long as contain the compound of alkene class unsaturated group and sulfonic acid group.Alkene class unsaturated group guarantees and other unit copolymerization that sulfonic acid group guarantees better water solubility.X can be selected from vinyl sulfonic acid, styrene sulfonic acid, 2-hydroxyl-3-allyloxy-1-propyl sulfonic acid, allyloxy benzene sulfonic acid, 2-acrylamido-2-methyl-propyl sulfonic acid, isoprene sulfonic acid etc.X in whole polymkeric substance shared ratio in 10%～30% molar ratio range, preferred 15%～25%.Be lower than 10% o'clock white space and keep on file easily, the ink affinity that is higher than 30% o'clock forme is not good.
As the copolymerization units of Y representative, be the acrylic or methacrylic acid copolymerization units that contains the side chain of two unsaturated double-bonds.The side chain that wherein contains two unsaturated double-bonds is by elder generation's grafting GMA monomer in acrylic or methacrylic acid, and then grafting alkene class unsaturated double-bond reaches on GMA.Can be used for the ethylenically unsaturated monomers of grafting can be selected from acryloyl chloride, methacrylic chloride, allyl isocyanate and isocyanate group ethyl-methyl acrylate etc.Y plays the effect of adjusting water wettability and photo-crosslinking curing rate in whole polymkeric substance, by on Y, introducing two unsaturated groups, can improve the ratio of unsaturated double-bond in the polymkeric substance greatly, among the present invention as required even can make the ratio of unsaturated double-bond in whole polymkeric substance reach 150%, laser curing velocity can be greatly improved like this, enough water wettabilities can be guaranteed again simultaneously.Y shared ratio in whole polymkeric substance is good in 20%～40% molar ratio range, preferred 25%～30%.
As the copolymerization units of Z representative, Z is acrylate or the methacrylic acid copolymerization units that contains a unsaturated double-bond substituted radical.Available acrylate can be selected from propenoic acid beta hydroxyl ethyl ester, methacrylic acid β hydroxyl ethyl ester, methylol methyl acrylate etc.The monomer of available grafting has acryloyl chloride, methacrylic chloride, allyl isocyanate and isocyanate group ethyl-methyl acrylate etc.Z the shared ratio of whole multipolymer 30%～50% molar ratio range in be good, preferred 35%～45%.
-(X)-(Y)-(Z)-the unsaturated water-soluble polymers of structure in, the unsaturated double-bond sum accounts for 60～80% mol ratios of polymkeric substance, preferred 65～75%.Be lower than at 60% o'clock, can not obtain high curing rate and high cross-linking density; Be higher than at 80% o'clock, unfavorable for the shelf stability of resin.
-(X)-(Y)-(Z)-the unsaturated water-soluble polymers of structure accounts for 40%～80% of whole photographic layer dry weight, preferred 50%-70%.Be lower than at 40% o'clock, the coating of blank parts is difficult for wiping, and disadvantage dirty on the blank position easily takes place; Be higher than at 80% o'clock, the coating ink affinity is not good, easily blind version.
The performed polymer of photopolymerization of the present invention can use various types of prepolymers, as polyesters esters of acrylic acid, epoxy acrylate class, urethane acrylate class, polyether acrylate class, organosilicon preformed polymer class etc., wherein be preferably polyurethane acroleic acid class performed polymer.This prepolymer accounts for 1～50% of the dry weight of filming in light sensitive layer be good, preferred 5%～30%.Consumption is lower than at 1% o'clock, and curing rate is low, and the coating ink affinity is not good; Consumption surpasses at 50% o'clock, and the site reduction is not good, and coating easily is clamminess.
Photopolymerizable monomer of the present invention can be used various types of monomers, as: the simple function group monomer has (methyl) acrylate such as ethyl acrylate, butyl acrylate, allyl acrylate etc.; Polyfunctional monomer, diacrylate, 1 is arranged, 6-hexanediyl ester, pentaerythritol triacrylate and tetraacrylate, 1,3,5 one three one (2 one acrylyl oxy-ethyl) isocyanuric acid esters, hydroxypropyl glycerine base triacrylate, hydroxyethyl trimethylolpropane triacrylate, polyethylene glycol dimethacrylate etc.; The isocyanate group monomer has 2 one isocyanic acid Jia Jibingxisuanyizhis and dimethyl one m one isopropenyl benzyl isocyanate ester etc. preferably use polyfunctional monomer. and polyfunctional monomer accounts for 1～80% of the dry weight of filming in light sensitive layer be good, preferred 10%～50%.
Photoinitiators of the present invention can be the single compound or composition of two or more components of planting.Preferably adopt when exposure and cause crosslinked photoinitiators because of producing free radical.Preferable photoinitiators has activity in exposure when 200 to 500nm (as ultraviolet, visible light and infrared radiation) following time.Best photoinitiators has activity 300 to 450nm the time.The suitable visible light and the photoinitiators of uv induction comprise, ketone such as benzil, benzoin and acyloin class, for example, 2,2 one dimethoxys, one 2 one phenyl acetophenone, 2-benzyl one 2-N, N one dimethylamino one 1-(the 4-beautiful jade is for benzyl)-1 one butanone and benzoin methyl ester (2 one methoxyls, one 2 one phenyl acetophenone) etc.; The diaryl group iodized salt of sensitization and triaryl sulfonium salts etc.; The halogenated methyl 1 that chromophore replaces, 3,5 one triaizine compounds etc.All these photoinitiators use separately or with suitable accelerator (as amine, superoxide, and phosphorus compound) and/or suitable light sensitizer (as, ketone or a one dione compounds such as camphorquinone) use together.Photoinitiators is preferably in has enough amounts to obtain required extent of polymerization in the structure of the present invention.This amount depends on the efficient of photoinitiators and the thickness of photoactive layer.Usually the content of photoinitiators is 0.01 to 20 (weight) of coating dry weight.The preferable content of photoinitiators is 0.5% to 15% of coating dry weight among the present invention, preferred 0.5% to 10%.
Lithographic plate selectable components is colorant and/or dyestuff or fuel system among the present invention.For visible image is arranged, can add colorant of people and/or dyestuff or fuel system after exposure.Compounds suitable for use or system can be exposed to when it under actinic radiation or when its change color or color and luster when product from the photoinitiators that exposes contact.Suitable compound or system include but is not limited to, and as a colourless dyestuff, as the thiazine of acyl group protection, diazine is with oxazine, hydrol (as the hydrol of Michler), indoles alkene and triarylmethane lactone (as Crystal Violet lactone).The content of dyestuff in lithographic plate of the present invention should be enough to obtain the required version exposed portion and the contrast of unexposed portion.The preferable content of dyestuff is 0 to 10% (weight) of coating.
And photosensitive composition of the present invention can contain the combination of the component of various materials and necessity of the present invention.For example, the dyestuff of pigment, organic or inorganic particle, sensitization, plastifier, cementing agent, surfactant, antioxidant, help paint, anti-stabilizing agent, wax, ultraviolet or visible light absorber and brightener to can be used for the present invention and do not influence its performance.
The used version base of the present invention is through electrolyzing and coarsening and anodic oxidation and carries out sealing of hole and handle the back aluminum substrate that its center line average boldness is at 0.4～0.6um.Preferred 0.3～0.5um.Version base like this can make by the method for various electrolyzing and coarsening.Aluminum substrate of the present invention is the high-purity aluminium plate, and its aluminium content is preferably in more than 99%.Suitable aluminum substrate is (being limited to this but lose): iron accounts for 0.1%～0.5%, silicon accounts for 0.03%～0.3%, copper accounts for 0.003%～0.03%, titanium accounts for 0.01%～0.1%.The used electrolytic solution of electrolyzing and coarsening can be the aqueous solution of acid, alkali or salt or the aqueous solution that contains organic solvent.Wherein, it is better to make electrolytic solution with the aqueous solution of hydrochloric acid, nitric acid or their salt.At first aluminium plate is placed in the aqueous solution of 1%～30% NaOH, potassium hydroxide, sodium carbonate, sodium silicate etc., under 20～80 ℃ temperature, carries out 5～250 seconds chemical corrosion.Then in 10～30% nitric acid or sulfuric acid with 20～70 ℃ temperature neutralization, to remove grey matter.Pass through the aluminium plate of cleaning like this, under 10～60 ℃ temperature, with square wave, bench-type ripple or the sine wave etc. of positive and negative interaction variation, with 5～100A/dm
2Current density, electrolytic treatments is 10～300 seconds in the electrolytic solution of nitric acid or hydrochloric acid.Then, the aluminium plate through electrolysis is carried out anodized.Sulfuric acid process is used in anodic oxidation usually.The concentration of the sulfuric acid that uses is 5～30%, and current density is 1～15A/dm
2, oxidizing temperature is at 20～60 ℃, and oxidization time is 5～250 seconds, to form 1～10g/m
2Oxide film. the oxide film of Xing Chenging has higher oxide film micropore usually like this; adsorptive power is stronger; so be easy to adhere to foul. also need to carry out sealing of hole usually and handle. sealing of hole is handled can use various methods, is good with 50%～80% volume that reaches sealing oxide film micropore.
Photosensitive composition of the present invention usually with the coating of this field known technology (as, cutter is coated with, blade coating, bar is coated with, roller coat, extrusion etc.) on the version base.Photosensitive composition of the present invention is dissolved in appropriate solvent or/and in the water, be made into coating fluid.Suitable solvent has: ethylene glycol ethyl ether, ethylene glycol monomethyl ether, diethylene glycol methyl ether, methyl lactate, ethyl lactate, MEK, 1-methoxyl-2-propyl alcohol etc.The coating dry weight is 0.2～10g/m
2The best coating weight of photosensitive composition coating is 0.5g/m
2～3g/m
2
Before coating photosensitive composition of the present invention, preferably on the version base of handling through sealing of hole, be coated with earlier the unsaturated water-soluble polymers of the present invention-(X)-(Y)-(Z)-structure.Coating process can use various methods, as cutter be coated with, blade coating, bar are coated with, roller coat, extrusion, bar seam extrusion coated etc.Before the coating-(X)-(Y)-(Z)-polymkeric substance of structure is soluble in water to be made into suitable concentration, perhaps add various coating additives and be adjusted to suitable painting parameter.The coating dry weight of hydrophilicity-imparting treatment is preferably in 0.01～100mg/dm
2Scope in, preferred 5～50mg/dm
2Be less than 0.01mg/dm
2, fall flat; Surpass 50mg/dm
2The time, the coating and the bonding force of version base are descended, easily cause disadvantages such as version.
Below by example explanation the present invention, but be not limited to these strength.
Synthesis example 1
The DMF that adds 210 milliliters in 500 milliliters there-necked flask makes solvent, adds acrylic acid 14.4 grams, methacrylic acid β hydroxyl ethyl ester 32.6 grams and 2-acrylamido-2-methyl propane sulfonic acid 10.35 grams then respectively.Such solution is feeding N
2Under the condition, warming while stirring adds the AIBN0.3 gram when temperature rises to 80 ℃, remain under this temperature and reacted 4.5 hours.Afterwards, in such solution, add the GMA10.66 gram, methoxyl phenol 0.1 gram and tetramethyl ammonium chloride 8.22 are restrained, continue to remain under 80 ℃, reacted 4.5 hours.Subsequently above-mentioned solution is cooled to 30 ℃, adds acryloyl chloride 29.41 gram again,, remained under 30 ℃ the temperature reaction 1.5 hours methoxyl phenol 0.3 gram, triethylamine 32.89 grams.At last above-mentioned solution is disperseed in methyl lactate, drying obtains about 90 water-soluble polymerss of the present invention 1 that restrain.
Synthesis example 2
The DMF that adds 210 milliliters in 500 milliliters there-necked flask makes solvent, adds acrylic acid 7.2 grams, methacrylic acid β hydroxyl ethyl ester 32.6 grams and 2-acrylamido-2-methyl propane sulfonic acid 31.05 grams then respectively.Such solution is feeding N
2Under the condition, warming while stirring adds the AIBN0.3 gram when temperature rises to 80 ℃, remain under this temperature and reacted 4.5 hours.Afterwards, in such solution, add the GMA3.55 gram, methoxyl phenol 0.04 gram and tetramethyl ammonium chloride 2..74 are restrained, continue to remain under 80 ℃, reacted 4.5 hours.Subsequently above-mentioned solution is cooled to 30 ℃, adds acryloyl chloride 24.89 gram again,, remained under 30 ℃ the temperature reaction 1.5 hours methoxyl phenol 0.25 gram, triethylamine 27.83 grams.At last above-mentioned solution is disperseed in methyl lactate, drying obtains about 92 water-soluble polymerss of the present invention 2 that restrain.
Synthesis example 3
The DMF that adds 210 milliliters in 500 milliliters there-necked flask makes solvent, adds acrylic acid 14.4 grams, propenoic acid beta hydroxyl ethyl ester 17.41 grams and 2-acrylamido-2-methyl propane sulfonic acid 31.05 grams then respectively.Such solution is feeding N
2Under the condition, warming while stirring adds the AIBN0.3 gram when temperature rises to 80 ℃, remain under this temperature and reacted 4.5 hours.Afterwards, in such solution, add the GMA17.77 gram, methoxyl phenol 0.18 gram and tetramethyl ammonium chloride 13.70 are restrained, continue to remain under 80 ℃, reacted 4.5 hours.Subsequently above-mentioned solution is cooled to 30 ℃, adds acryloyl chloride 24.89 gram again,, remained under 30 ℃ the temperature reaction 1.5 hours methoxyl phenol 0.25 gram, triethylamine 27.83 grams.At last above-mentioned solution is disperseed in methyl lactate, drying obtains about 88 grams water-soluble polymers 3 of the present invention.
Synthesis example 4
The DMF that adds 210 milliliters in 500 milliliters there-necked flask makes solvent, adds acrylic acid 10.8 grams, propenoic acid beta hydroxyl ethyl ester 26.11 grams and 2-acrylamido-2-methyl propane sulfonic acid 25.88 grams then respectively. and such solution is feeding N
2Under the condition, warming while stirring adds the AIBN0.3 gram when temperature rises to 80 ℃, remain under this temperature and reacted 4.5 hours.Afterwards, in such solution, add the GMA8.89 gram, methoxyl phenol 0.1 gram and tetramethyl ammonium chloride 6.85 are restrained, continue to remain under 80 ℃, reacted 4.5 hours.Subsequently above-mentioned solution is cooled to 30 ℃, adds acryloyl chloride 26.06 gram again,, remained under 30 ℃ the temperature reaction 1.5 hours methoxyl phenol 0.26 gram, triethylamine 29.15 grams.At last above-mentioned solution is disperseed in methyl lactate, drying obtains about 90 water-soluble polymerss of the present invention 4 that restrain.
Synthesis example 5
The DMF that adds 210 milliliters in 500 milliliters there-necked flask makes solvent, adds acrylic acid 14.4 grams, propenoic acid beta hydroxyl ethyl ester 23.21 grams and 2-acrylamido-2-methyl propane sulfonic acid 20.7 grams then respectively.Such solution is feeding N
2Under the condition, warming while stirring adds the AIBN0.3 gram when temperature rises to 80 ℃, remain under this temperature and reacted 4.5 hours.Afterwards, in such solution, add the GMA14.22 gram, methoxyl phenol 0.15 gram and 4-ammonio methacrylate 11 are restrained, continue to remain under 80 ℃, reacted 4.5 hours.Subsequently above-mentioned solution is cooled to 30 ℃, adds acryloyl chloride 27.15 gram again,, remained under 30 ℃ the temperature reaction 1.5 hours methoxyl phenol 0.3 gram, triethylamine 30.36 grams.At last above-mentioned solution is disperseed in methyl lactate, drying obtains about 86 grams water-soluble polymers 5 of the present invention.
The preparation of version base: the A1050 calendering aluminium plate of purity 99.5%, thick 0.3mm, 70 ℃ of following etches are 20 seconds in 5% sodium hydrate aqueous solution, after the flowing water flushing, neutralize with 1% aqueous solution of nitric acid immediately.In 1% aqueous hydrochloric acid solution, use sine wave alternating current with 50A/dm down for 40 ℃ then
2Current density electrolyzing and coarsening 16 seconds.Then under 40 ℃, with in 5% the sodium hydrate aqueous solution with 10 seconds.Washing.Under 30 ℃, the aqueous sulfuric acid with 20% is with 15A/dm at last
2Current density, anodic oxidation 20 seconds.Washing.80 ℃ are carried out sealing of hole with 5% sodium silicate aqueous solution down and handled 18 seconds.Washing.Dry.The version base that obtains like this, the center line average boldness is 0.5um, the heavy 3.0g/dm of oxide film
2
Hydrophilicity-imparting treatment: on the version base that obtains in the above, the aqueous solution of the water soluble resin of the present invention of coating 0.1%, 100 ℃ were descended dry 20 seconds, and obtained 20mg/m
2The coating dry weight.
Above-mentioned through the version base of hydrophilicity-imparting treatment on sensitization liquid below the extrusion coated, then 120 ℃ dry 30 seconds down.Obtain 1.5g/m
2The coating dry weight.
Sensitization liquid 1 (each component by weight)
Water-soluble polymers 1 1.6 of the present invention
Polyurethane acroleic acid prepolymer 0.64
Pentaerythritol triacrylate 0.86
2-(4-methoxy-naphthyl)-4, two (three chloro the methyl)-1,3,5-triazines 0.03 of 6-
P methoxy phenol 0.03
BYK-306 0.012
Phthalocyanine blue dyestuff 0.032
1-methoxyl-2-propyl alcohol 32.80
The plate that obtains like this light value with 60 on the platemaking machine of UC-SETTER741 type UV-CTP exposes.Then, in MASTER VIEW developing machine,,, lock up printing then with pure tap water flushing 30 seconds～50 seconds with 40 ℃ temperature.Also can directly lock up on the printing machine and print without the tap water flushing.Its performance is listed in the table one of back.
With top identical method preparation version base, hydrophilic layer and painting photosensitive liquid.The following component of sensitization liquid:
Sensitization liquid 2 (each component by weight)
Water-soluble polymers 2 1.6 of the present invention
Polyurethane acroleic acid prepolymer 0.64
Pentaerythritol triacrylate 0.86
2-(4-methoxy-naphthyl)-4, two (three chloro the methyl)-1,3,5-triazines 0.03 of 6-
P methoxy phenol 0.03
BYK-306 0.012
Phthalocyanine blue dyestuff 0.032
1-methoxyl-2-propyl alcohol 32.80
The plate that obtains like this light value with 80 on the platemaking machine of UC-SETTER741 type UV-CTP exposes.Then, in MASTER VIEW developing machine,,, lock up printing then with pure tap water flushing 30 seconds～50 seconds with 40 ℃ temperature.Also can wash, directly lock up on the printing machine and print without tap water.Its performance is listed in the table one of back.
With top identical method preparation version base, hydrophilic layer and painting photosensitive liquid.The following component of sensitization liquid:
Sensitization liquid 3 (each component by weight)
Water-soluble polymers 3 1.6 of the present invention
Polyurethane acroleic acid prepolymer 0.64
Pentaerythritol triacrylate 0.86
2-(4-methoxy-naphthyl)-4, two (three chloro the methyl)-1,3,5-triazines 0.03 of 6-
P methoxy phenol 0.03
BYK-306 0.012
Phthalocyanine blue dyestuff 0.032
1-methoxyl-2-propyl alcohol 32.80
The plate that obtains like this light value with 60 on the platemaking machine of UC-SETTER741 type UV-CTP exposes.Then, in MASTER VIEW developing machine,,, lock up printing then with pure tap water flushing 30 seconds～50 seconds with 40 ℃ temperature.Also can wash, directly lock up on the printing machine and print without tap water.Its performance is listed in the table one of back.
Embodiment 4
With top identical method preparation version base, hydrophilic layer and painting photosensitive liquid.The following component of sensitization liquid:
Sensitization liquid 4 (each component by weight)
Water-soluble polymers 4 1.6 of the present invention
Polyurethane acroleic acid prepolymer 0.64
Pentaerythritol triacrylate 0.86
2-(4-methoxy-naphthyl)-4, two (three chloro the methyl)-1,3,5-triazines 0.03 of 6-
P methoxy phenol 0.03
BYK-306 0.012
Phthalocyanine blue dyestuff 0.032
1-methoxyl-2-propyl alcohol 32.80
The plate that obtains like this light value with 70 on the platemaking machine of UC-SETTER741 type UV-CTP exposes.Then, in MASTER VIEW developing machine,,, lock up printing then with pure tap water flushing 30 seconds～50 seconds with 40 ℃ temperature.Also can wash, directly lock up on the printing machine and print without tap water.Its performance is listed in the table one of back.
Embodiment 5
With top identical method preparation version base, hydrophilic layer and painting photosensitive liquid.The following component of sensitization liquid:
Sensitization liquid 5 (each component by weight)
Water-soluble polymers 5 1.6 of the present invention
Polyurethane acroleic acid prepolymer 0.64
Pentaerythritol triacrylate 0.86
2-(4-methoxy-naphthyl)-4, two (three chloro the methyl)-1,3,5-triazines 0.03 of 6-
P methoxy phenol 0.03
BYK-306 0.012
Phthalocyanine blue dyestuff 0.032
1-methoxyl-2-propyl alcohol 32.80
The plate that obtains like this light value with 60 on the platemaking machine of UC-SETTER741 type UV-CTP exposes.Then, in MASTER VIEW developing machine,,, lock up printing then with pure tap water flushing 30 seconds～50 seconds with 40 ℃ temperature.Also can wash, directly lock up on the printing machine and print without tap water.Its performance is listed in the table one of back.
Embodiment 6
With method preparation version base, hydrophilic layer and the painting photosensitive liquid identical with example 1.Just adjust electrolysis electricity make the version a basic center line average boldness be 0.4um.
The plate that obtains like this light value with 60 on the platemaking machine of UC-SETTER741 type UV-CTP exposes.Then, in MASTER VIEW developing machine,,, lock up printing then with pure tap water flushing 30 seconds～50 seconds with 40 ℃ temperature.Also can wash, directly lock up on the printing machine and print without tap water.Its performance is listed in the table one of back.
Embodiment 7
With method preparation version base, hydrophilic layer and the painting photosensitive liquid identical with example 1.Just adjust electrolysis electricity make the version a basic center line average boldness be 0.6um.
The plate that obtains like this light value with 60 on the platemaking machine of UC-SETTER741 type UV-CTP exposes.Then, in MASTER VIEW developing machine,,, lock up printing then with pure tap water flushing 30 seconds～50 seconds with 40 ℃ temperature.Also can wash, directly lock up on the printing machine and print without tap water.Its performance is listed in the table one of back.
Embodiment 8
With method preparation version base, hydrophilic layer and the painting photosensitive liquid identical with example 1.The dry weight of just adjusting hydrophilic layer is 5mg/dm
2
The plate that obtains like this light value with 60 on the platemaking machine of UC-SETTER741 type UV-CTP exposes.Then, in MASTER VIEW developing machine,,, lock up printing then with pure tap water flushing 30 seconds～50 seconds with 40 ℃ temperature.Also can wash, directly lock up on the printing machine and print without tap water.Its performance is listed in the table one of back.
Embodiment 9
With method preparation version base, hydrophilic layer and the painting photosensitive liquid identical with example 1.The dry weight of just adjusting hydrophilic layer is 50mg/dm
2
The plate that obtains like this light value with 60 on the platemaking machine of UC-SETTER741 type UV-CTP exposes.Then, in MASTER VIEW developing machine,,, lock up printing then with pure tap water flushing 30 seconds～50 seconds with 40 ℃ temperature.Also can wash, directly lock up on the printing machine and print without tap water.Its performance is listed in the table one of back.
Comparative example 1
With method preparation version base, hydrophilic layer and the painting photosensitive liquid identical with example 1.Be the following component of sensitization liquid:
Sensitization liquid 6 (each component by weight)
Water-soluble polymers 1 1.6 of the present invention
Acrylic polymer 0.64
Pentaerythritol triacrylate 0.86
2-(4-methoxy-naphthyl)-4, two (three chloro the methyl)-1,3,5-triazines 0.03 of 6-
P methoxy phenol 0.03
BYK-306 0.012
Phthalocyanine blue dyestuff 0.032
1-methoxyl-2-propyl alcohol 32.80
The plate that obtains like this light value with 120 on the platemaking machine of UC-SETTER741 type UV-CTP exposes.Then, in MASTER VIEW developing machine,,, lock up printing then with pure tap water flushing 30 seconds～50 seconds with 40 ℃ temperature.Also can wash, directly lock up on the printing machine and print without tap water.Its performance is listed in the table one of back.
Comparative example 2
With method preparation version base, hydrophilic layer and the painting photosensitive liquid identical with example 1.Be the following component of sensitization liquid:
Sensitization liquid 7 (each component by weight)
Water-soluble polymers 1 1.6 of the present invention
Polyurethane acroleic acid prepolymer 0.64
Ethyl acrylate 0.86
2-(4-methoxy-naphthyl)-4, two (three chloro the methyl)-1,3,5-triazines 0.03 of 6-
P methoxy phenol 0.03
BYK-306 0.012
Phthalocyanine blue dyestuff 0.032
1-methoxyl-2-propyl alcohol 32.80
The plate that obtains like this light value with 110 on the platemaking machine of UC-SETTER741 type UV-CTP exposes.Then, in MASTER VIEW developing machine,,, lock up printing then with pure tap water flushing 30 seconds～50 seconds with 40 ℃ temperature.Also can wash, directly lock up on the printing machine and print without tap water.Its performance is listed in the table one of back.
Comparative example 3
With method preparation version base, hydrophilic layer and the painting photosensitive liquid identical with example 1.Be the following component of sensitization liquid:
Sensitization liquid 8 (each component by weight)
Water-soluble polymers 1 1.6 of the present invention
Polyurethane acroleic acid prepolymer 0.64
Pentaerythritol triacrylate 0.86
1-hydroxy-ketone (DAROCUR4265) 0.03
P methoxy phenol 0.03
BYK-306 0.012
Phthalocyanine blue dyestuff 0.032
1-methoxyl-2-propyl alcohol 32.80
The plate that obtains like this light value with 150 on the platemaking machine of UC-SETTER741 type UV-CTP exposes. then, in MASTER VIEW developing machine,,, lock up printing then with pure tap water flushing 30 seconds～50 seconds with 40 ℃ temperature.Also can wash, directly lock up on the printing machine and print without tap water.Its performance is listed in the table one of back.
Comparative example 4
With method preparation version base, hydrophilic layer and the painting photosensitive liquid identical with example 1.Just adjusting electrolysis electricity, to make the center line average boldness of version base be 0.3um.
The plate that obtains like this light value with 60 on the platemaking machine of UC-SETTER741 type UV-CTP exposes.Then, in MASTER VIEW developing machine,,, lock up printing then with pure tap water flushing 30 seconds～50 seconds with 40 ℃ temperature.Also can wash, directly lock up on the printing machine and print without tap water.Its performance is listed in the table one of back.
Comparative example 5
With method preparation version base, hydrophilic layer and the painting photosensitive liquid identical with example 1.Just adjusting electrolysis electricity, to make the center line average boldness of version base be 0.7um.
The plate that obtains like this light value with 60 on the platemaking machine of UC-SETTER741 type UV-CTP exposes.Then, in MASTER VIEW developing machine,,, lock up printing then with pure tap water flushing 30 seconds～50 seconds with 40 ℃ temperature.Also can wash, directly lock up on the printing machine and print without tap water.Its performance is listed in the table one of back.
Comparative example 6
With method preparation version base, hydrophilic layer and the painting photosensitive liquid identical with example 1.Be the following component of sensitization liquid:
Sensitization liquid 1 (each component by weight)
PVP(K60) 1.6
Polyurethane acroleic acid prepolymer 0.64
Pentaerythritol triacrylate 0.86
2-(4-methoxy-naphthyl)-4, two (three chloro the methyl)-1,3,5-triazines 0.03 of 6-
P methoxy phenol 0.03
BYK-306 0.012
Phthalocyanine blue dyestuff 0.032
1-methoxyl-2-propyl alcohol 32.80
The plate that obtains like this light value with 200 on the platemaking machine of UC-SETTER741 type UV-CTP exposes.Then, in MASTER VIEW developing machine,,, lock up printing then with pure tap water flushing 30 seconds～50 seconds with 40 ℃ temperature.Also can wash, directly lock up on the printing machine and print without tap water.Its performance is listed in the table one of back.
Comparative example 7
With method preparation version base, hydrophilic layer and the painting photosensitive liquid identical with example 1.The dry weight of just adjusting hydrophilic layer is 3mg/dm
2
The plate that obtains like this light value with 60 on the platemaking machine of UC-SETTER741 type UV-CTP exposes.Then, in MASTER VIEW developing machine,,, lock up printing then with pure tap water flushing 30 seconds～50 seconds with 40 ℃ temperature.Also can wash, directly lock up on the printing machine and print without tap water.Its performance is listed in the table one of back.
Comparative example 8
With method preparation version base, hydrophilic layer and the painting photosensitive liquid identical with example 1.The dry weight of just adjusting hydrophilic layer is 70mg/dm
2
The plate that obtains like this light value with 60 on the platemaking machine of UC-SETTER741 type UV-CTP exposes.Then, in MASTER VIEW developing machine,,, lock up printing then with pure tap water flushing 30 seconds～50 seconds with 40 ℃ temperature. also can wash, directly lock up on the printing machine and print without tap water. its performance is listed in the table one of back.
Table one
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200610128285A CN101192004B (en) | 2006-11-27 | 2006-11-27 | Chemical processing-free negative graph photosensitive composition suitable for UV-CTP and planographic printing plate manufactured therefor and planographic printing plate manufacture method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200610128285A CN101192004B (en) | 2006-11-27 | 2006-11-27 | Chemical processing-free negative graph photosensitive composition suitable for UV-CTP and planographic printing plate manufactured therefor and planographic printing plate manufacture method |
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| Publication Number | Publication Date |
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| CN101192004A CN101192004A (en) | 2008-06-04 |
| CN101192004B true CN101192004B (en) | 2010-05-12 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN200610128285A Expired - Fee Related CN101192004B (en) | 2006-11-27 | 2006-11-27 | Chemical processing-free negative graph photosensitive composition suitable for UV-CTP and planographic printing plate manufactured therefor and planographic printing plate manufacture method |
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Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101881929A (en) * | 2010-06-22 | 2010-11-10 | 刘华礼 | Method for preparing rinse-free negative image CTP plate |
| CN102540709B (en) * | 2010-12-30 | 2014-05-07 | 乐凯华光印刷科技有限公司 | Infrared sensitive chemistry-free light-sensing composition and lithographic printing plate made from same |
| JP5186574B2 (en) * | 2011-02-28 | 2013-04-17 | 富士フイルム株式会社 | Planographic printing plate precursor and plate making method |
| CN103728915B (en) * | 2013-12-19 | 2016-12-07 | 杭州电子科技大学 | A kind of CTP forme rinses dynamic control method |
| KR20210102494A (en) * | 2014-05-21 | 2021-08-19 | 아사히 가세이 가부시키가이샤 | Photosensitive resin composition and method for forming circuit pattern |
| CN106054524A (en) * | 2016-06-23 | 2016-10-26 | 成都新图新材料股份有限公司 | Photoresist for CTP plate aluminum plate base |
| CN106054525A (en) * | 2016-06-23 | 2016-10-26 | 成都新图新材料股份有限公司 | Chemistry-free negative image photosensitive composite suitable for UV-CTP |
| CN106125505A (en) * | 2016-06-23 | 2016-11-16 | 成都新图新材料股份有限公司 | A kind of photosensitive layer for UV CTP |
| JP7114860B2 (en) * | 2017-03-27 | 2022-08-09 | 東洋インキＳｃホールディングス株式会社 | Photosensitive coloring composition and color filter |
| CN108388083A (en) * | 2017-12-28 | 2018-08-10 | 江苏乐彩印刷材料有限公司 | A kind of manufacturing method for exempting to handle negative image CTCP editions |
| CN109878234B (en) * | 2019-01-22 | 2021-05-07 | 安徽强邦印刷材料有限公司 | Multi-coating water development type treatment-free direct-loading printing plate |
| CN112976859B (en) * | 2019-12-16 | 2023-03-10 | 乐凯华光印刷科技有限公司 | Negative lithographic printing plate precursor and negative lithographic printing plate |
| CN113954502B (en) * | 2021-10-26 | 2023-04-07 | 浙江康尔达新材料股份有限公司 | Photosensitive negative-working lithographic printing plate precursor and method for making lithographic printing plate by using the same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1664698A (en) * | 2004-03-04 | 2005-09-07 | 富士胶片株式会社 | Polymerizable composition and lithographic printing plate precursor |
| EP1596253A1 (en) * | 2003-02-19 | 2005-11-16 | Asahi Kasei Chemicals Corporation | Process for producing water development printing plate for relief printing |
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2006
- 2006-11-27 CN CN200610128285A patent/CN101192004B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1596253A1 (en) * | 2003-02-19 | 2005-11-16 | Asahi Kasei Chemicals Corporation | Process for producing water development printing plate for relief printing |
| CN1664698A (en) * | 2004-03-04 | 2005-09-07 | 富士胶片株式会社 | Polymerizable composition and lithographic printing plate precursor |
Non-Patent Citations (2)
| Title |
|---|
| JP特开2005-202150A 2005.07.28 |
| JP特开2006-251356A 2006.09.21 |
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