CN104742557A - Water-developable chemistry-free thermosensitive board and preparation method thereof - Google Patents
Water-developable chemistry-free thermosensitive board and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a water-developable chemistry-free thermosensitive board and a preparation method thereof. The water-developable chemistry-free thermosensitive board is environment-friendly, and by the water-developable chemistry-free thermosensitive board, cationic cross linking and free radical polymerization can be generated simultaneously. The technical problem that the water-developable capability and the pressing resistance of a chemistry-free thermosensitive CTP (computer-to-plate) board in the prior art is solved. The water-developable chemistry-free thermosensitive board comprises a supporting body, a thermosensitive layer and a protecting layer; and the thermosensitive layer comprises the following raw materials in part by weight: 30-70 parts of water-soluble thermo-crosslinking copolymers, 10-50 parts of performed polymers containing hydrophilic radicals, 10-30 parts of polyfunctional monomers, 1-20 parts of cationic initiators and 1-20 parts of infrared radiation absorption dyes. By the technical scheme, water development can be carried out directly after infrared laser scanning imaging is performed, imaging contrast is high, boards can be detected before being machined, and printing resistance is high.
Description
Technical field
The present invention relates to lithography technique field, be specifically related to a kind of aqueous developable and exempt from chemical treatment temperature-sensitive version and preparation method thereof.
Background technology
Lithography technique moves towards CTP technology (being called for short CTP technology) from traditional laser photo film copy PS platemaking technology comprehensively, and CTP plate is also popularized gradually.CTP plate kind is a lot, and relatively more universal comprises Silver Salt Diffusion Transfer CTP Plate material, UV-CTP version, purple laser polymerization CTP plate, thermal CTP plate material etc.Wherein most popular is thermal CTP plate material.
The process that the developer solution that CTP plate-making technology needs a use to contain multiple toxic organic compound or highly basic develops, also exists poisonous and harmful liquid waste processing and brings environmental problem.At present, the focus that Development of New Generation is green, the plate exploitation of the chemical treatment CTP Ban Shi world is exempted from environmental protection.
Developing green, environmental protection exempt from chemical treatment CTP platemaking technology route a lot, can be divided into thermal ablation technology, polarity turns technology and hot-melt technology.
Thermal ablation technology plate adopts aluminum plate foundation or polyester-based, utilizes plasma metal deposition technique to prepare plate.But there is scrap problems in ablation plate.Presstek company has delivered the ablation plate with sandwich, solves ablation scrap problems.Agfa Corp. develops the ablation technology non-processor CTP version with deposited silver layer, this plate by have water-wetted surface support (aluminium, PET), can be ablated metal deposition layer and crosslinked hydrophobic layer form.Metal deposition layer is the metal film utilizing metal deposition technique to be formed, and this metal can be silver, titanium etc.Crosslinked hydrophobic layer, by radiation or heat cure, makes unsaturated monomer be cross-linked, also can be cross-linked to form cured layer by heat-sensitive resin, or obtains by the process of sense fat liquid.Infrared laser power causes the Argent grain in silver layer that capillary change occurs, form fluffy Argent grain, remain in plate on the surface, thus be easy to remove residue with vacuum suction or liquid, expose aluminium plate water-wetted surface and form hydrophilic area, and unexposed cross-linked layer is insoluble to liquid, form oleophylic district.
Polarity conversion technology: plate is made up of support and thermographic layer.Thermographic layer contains photo-thermal and changes agent and the convertible polymer of temperature-sensitive (as poly-oxinane methacrylate, with aryldiazosulphonate base ethylene copolymer).The convertible polymer of temperature-sensitive is adopted to form thermo-sensitive material.Before imaging, the water-soluble solution of heat-sensitive layer.During imaging, infrared light radiation absorbing dye absorbing laser energy, the heat of generation causes diazo to decompose, and makes to be exposed temperature-sensitive copolymer and becomes hydrophobic from hydrophilic, thus form oleophylic district.And unexposed area temperature-sensitive copolymer is still water-soluble, thus form hydrophilic area.The factor restricting this technical development remains printability.Its ink part is all medicine membrane coat, and printing controls all to be subject to severely restricts with pressrun, realizes the application of real large-scale commercial and also has larger distance.
Hot-melt technology: thermographic mid-infrared light radiation absorbing dye is converted into heat energy laser energy, the heat produced makes the temperature of the thermoplastic polymer particles be dispersed in crosslinked hydrophilic layer higher than its gel humidity, cause thermoplastic polymer particles generation agglutinating reaction, exposure region becomes hydrophobic oleophilic oil by hydrophily.And unexposed area is still dissolved in the aqueous solution of PH >=4, form hydrophilic area.Its forme blank parts is aluminium base after frosted and oxidation processes, instead of medicine membrane coat, and printability and common plate are without any difference.
Exempt from process temperature-sensitive version be included in machine treatment technology and exempt from chemical treatment method.
At machine treatment technology, its principle is: precoating planographic printing plate material is after making a plate by the scanning of CTP platemaking machine, its unnecessary coating for the blank position of printing is on the printer by removing under the effect of damping water and ink, walked by transferring paper tape after unnecessary coating removal, blank position is hydrophilic aluminum substrate, and this mode achieves the environmental protection object of lithography process without emissions.But owing to being directly printed on the machine after the exposure of such plate, inconvenience carries out the detection before upper machine with after developing machine development to the image on plate as traditional CT P plate, carry out image detection so that detect before locing up printing machine and identify various color version when locing up on printing machine, prevent the phenomenon of printing images mistake and wrongly installed color version position from occurring, have certain use limitation.
Another kind of mode claims " exempting from chemical treatment " technology.What be representative with aqueous developable technology exempts from chemical treatment temperature-sensitive platemaking technology, the advantage of this mode had both achieved the effect comparing environment protection emission, also as conventional CTP plate, the correction of site can be carried out before sensitive lithographic plate is printed on the machine, in order to avoid sensitive lithographic plate becomes blind version after machine more simultaneously.
Chemical treatment CTP version is exempted from exploitation, and one of key technology is the exploitation of plate precursor and function organic composition.EP0980754 describes carboxyl decarboxylation and realizes hydrophilic-hydrophobic conversion techniques, but phase in version compound molecular weight is too large, and energy threshold becomes large, and decarboxylation difficulty, so this technology plate pressrun is poor.WO94/23954 describes a kind of microcapsules hot-melt technology, and laser hot melt makes microcapsules destroy, and hydrophilic substance destruction transfers to hydrophobic, but damaged thing easily causes printing blank space to pollute; US4004924 introduces the mixture of a kind of thermoplastic hydrophobic's particle and hydrophilic adhesive, but not resistance to print; Ai Kefa EP 2006-5-24 06114475.4 introduces a kind of semicontinuous emulsion method and manufactures styrene, acrylonitrile emulsion thermoplastic granulates, hot melt can be realized, but not containing self-emulsifying hydrophilic radical, Grain size controlling technical requirement is high, emulsification stability of emulsion is poor, anti-micro-raw agent need be added, the material assistance developments such as exhibiting high surface active material and developing rubber need be added during development, produce a large amount of development waste liquid; Kodak US 2005-8-3 11/196,124, introduce a kind of hydrophilic binding agent, molecule is one-dimensional linear structure, and pressrun is not high; Kodak US 2006-7-27 11/494,235 introduces a kind of containing hydrophilic group with containing allyl ester side chain, is that condensation reaction under alkali effect forms by carboxyl side group and allyl halide, but side reaction by-products is more, post processing bothers, and hydrophily is poor, and ester group still not resistance to print.
At present, improve the performance that aqueous developable exempts from chemical treatment heat-sensitive CTP plate further, the water development ability and the Nai Yin ability that particularly improve plate are the focuses that water development exempts from the exploitation of chemical treatment thermal CTP plate material.
Summary of the invention
The technical problem to be solved in the present invention be existing exempt to exist in chemical treatment heat-sensitive CTP plate technology plate water development ability and Nai Yin ability, there is provided one cationic crosslinked and radical polymerization can occur simultaneously, the aqueous developable of environmental protection exempts from chemical treatment temperature-sensitive version and preparation method thereof.
For achieving the above object; the present invention adopts following technical proposals: a kind of aqueous developable exempts from chemical treatment temperature-sensitive version; it comprises support, heat-sensitive layer and protective layer, and described heat-sensitive layer comprises the raw material of following weight parts meter: water soluble thermo-crosslinked copolymer 30-70 part, the performed polymer 10-50 part containing hydrophilic group, polyfunctional monomer 10-30 part, cationic initiator 1-20 part, infrared light radiation absorbing dye 1-20 part.
Described heat-sensitive layer comprises the raw material of following weight parts meter: water soluble thermo-crosslinked copolymer 40-60 part, the performed polymer 20-40 part containing hydrophilic group, polyfunctional monomer 15-20 part, cationic initiator 5-15 part, infrared light radiation absorbing dye 5-15 part.
Described water soluble thermo-crosslinked copolymer has following structure:
Wherein, R1, R2, R4 are H atom or methyl; R3 is
or
r5 is O atom or OCH2CH2NHCOO, n is the integer of 20-60; A, b, c, d are the weight portion of corresponding copolymerization units, and weight portion shared by a is 40-70 part, and weight portion shared by b is 10-30 part, and weight portion shared by c is 10-30 part, and weight portion shared by d is 10-30 part.
The described performed polymer containing hydrophilic group has following structure:
Described polyfunctional monomer is polyfunctional group acrylic monomer or polyfunctional group polyurethane acroleic acid class monomer.
Described cationic initiator is salt compounded of iodine, the one of sulfosalt or at least two kinds; Cationic initiator heat decomposition temperature is 150-200 DEG C.
Described infrared light radiation absorbing dye is the cyanine dyes of absworption peak at 750-850nm.
Described heat-sensitive layer coating dry weight is 8-15mg/dm
2, described protective layer dry weight is 5-20mg/dm
2.
Aqueous developable exempts from a preparation method for chemical treatment temperature-sensitive version, it is characterized in that: it comprises the following steps: (1) process aluminum substrate support; (2) coated heat photosensitive layer on aluminum substrate support after treatment; (3) coat protective layer on heat-sensitive layer.
Described process aluminum substrate support comprises the electrolyzing and coarsening of aluminum substrate support and anodic oxidation and the sealing pores that carries out, and after process, aluminum substrate support center line average boldness is 0.4-0.6 μm.
Can there is cationic crosslinked and radical polymerization, environmental protection in the present invention, speed is high, site is Well-recovered simultaneously, can direct water development after with infrared laser scanning imagery, and imaging contrast is high, the inspection version before being available on the machine, and can obtain high pressrun.There is dual imaging capability, cationic crosslinked and radical polymerization can be realized simultaneously.LASER HEAT energy passes through infrared light radiation absorbing dye by energy trasfer to cationic initiator, cationic initiator produces heterolytic fission and homolysis, heterolytic fission releases cation, make the epoxy radicals cross-linked polymeric in water soluble thermo-crosslinked copolymer, the free radical that homolysis produces simultaneously makes the performed polymer and the polyfunctional monomer generation radical polymerization that contain hydrophilic group, realize dual thermographic, be cross-linked with single epoxy radicals or compared with radical polymerization, improve imaging capability and the pressrun of plate; Plate contains two kinds of hydrophilic row functional compounds, water soluble thermo-crosslinked copolymer contains esterification and hangs polyether-based, and the performed polymer containing hydrophilic group contains bis-phenol structure carboxyl, and these two kinds of hydrophilic groups all have very high space stretching, there is very strong hydrophily, improve the water development ability of plate.After use thermosensitive CTP platemaking machine scan exposure, can direct water development.
Detailed description of the invention
A kind of aqueous developable exempts from chemical treatment temperature-sensitive version; it comprises support, heat-sensitive layer and protective layer, and described heat-sensitive layer comprises the raw material of following weight parts meter: water soluble thermo-crosslinked copolymer 30-70 part, the performed polymer 10-50 part containing hydrophilic group, polyfunctional monomer 10-30 part, cationic initiator 1-20 part, infrared light radiation absorbing dye 1-20 part.
Described heat-sensitive layer comprises the raw material of following weight parts meter: water soluble thermo-crosslinked copolymer 40-60 part, the performed polymer 20-40 part containing hydrophilic group, polyfunctional monomer 15-20 part, cationic initiator 5-15 part, infrared light radiation absorbing dye 5-15 part.
Described water soluble thermo-crosslinked copolymer has following structure:
Wherein, R1, R2, R4 are H atom or methyl; R3 is
or
r5 is O atom or OCH2CH2NHCOO, n is the integer of 20-60; A, b, c, d are the weight portion of corresponding copolymerization units, and weight portion shared by a is 40-70 part, and weight portion shared by b is 10-30 part, and weight portion shared by c is 10-30 part, and weight portion shared by d is 10-30 part.
Design a kind of Thermal sensitive plate, first it is considered that the heat-sensitive layer of plate, in heat-sensitive layer, need a kind of important binding agent and functional film-forming resin, functional film-forming resin can after guarantee coating fluid drying film forming, heat-sensitive layer is attached on support.Binding agent can be solution state, also can be emulsion state.Containing functional group on functional film-forming resin, bear specific function effect, containing water-soluble heat cross-linking copolymer of the present invention is exactly this type of binding agent.
Most of temperature-sensitive version functional resin all devises thermoplastic styrene construction unit on resin structure, and water soluble thermo-crosslinked copolymer of the present invention is also containing thermoplastic styrene construction unit.As everyone knows, styrol structural unit has good lipophile, thermoplasticity, glass transition temperature is higher, styrol copolymer has the easier hot melt of heated portion as exempting from chemical treatment heat-sensitive CTP plate binding agent, arrange more tight between molecule, thermal imagery part is more firm, and good rigidity, can increase the advantage of plate pressrun.Synthesize multiple copolymer of the present invention, the weight portion of styrenic interpolymerized units in water soluble thermo-crosslinked copolymer is 40-70 part.
Design a kind of CTP version binding agent, select outstanding hydrophobic segment to be necessary.Cyano group is more outstanding hydrophobic group.Good lipophile of the present invention introduces hydrophobic side chain cyano group, after water soluble thermo-crosslinked copolymer introduces hydrophobic side chain cyano group, has good pliability, drug resistance and hydrophobicity as binding agent thermal polymerization imaging moiety.The method that multiple copolymer of the present invention introduces hydrophobic side chain radical nitrile is in copolymerization component, devise the vinyl component construction unit of side chain containing base nitrile, preferred acrylonitrile or methacrylonitrile or their mixture.Synthesize multiple copolymer of the present invention, the weight portion of (methyl) acrylonitrile compolymer unit in water soluble thermo-crosslinked copolymer is 10-30 part.
The plate of the present invention's design has cationic crosslinked ability, infrared laser thermal energy passes through infrared light radiation absorbing dye by energy trasfer to cationic initiator, cationic initiator produces heterolytic fission and homolysis, heterolytic fission releases cation, makes the epoxy radicals cross-linked polymeric in water soluble thermo-crosslinked copolymer.The water soluble thermo-crosslinked copolymer of the present invention devises the copolymerization units containing side chain epoxy radicals structure in copolymerization component, realize resin side chain and hang epoxy radicals, the present invention introduces side chain epoxy in water soluble thermo-crosslinked copolymer structure chain, select acrylic monomer containing epoxy radicals as copolymerization units, acrylic monomer containing epoxy radicals has a lot, as glycidyl acrylate, GMA, 3, 4-expoxycyclohexyl acrylate, 3, 4-epoxycyclohexylmethyl acrylate etc., the present invention is preferably containing the acrylic monomer of epoxy radicals, object lesson is as follows:
The weight portion of copolymerization units in water soluble thermo-crosslinked copolymer containing side chain epoxy radicals structure is 10-30 part.
As exempting from chemical treatment CTP version hydrophilic agglomerant, water soluble thermo-crosslinked copolymer of the present invention contains hydrophilic structural unit, and after infrared laser scanning imagery, heat-sensitive layer molecular weight sharply becomes large, make coating more firm, the coating after LASER HEAT exposure is difficult to be removed by water and ink; Owing to there is water soluble thermo-crosslinked copolymer and the performed polymer containing hydrophilic group in the unnecessary coating at unexposed blank position, be easy to be removed by water, exposing blank position after unnecessary coating removal is hydrophilic aluminum substrate, achieves the environmental protection object of lithography process without emissions.The water soluble thermo-crosslinked copolymer of the present invention devises polyethers hydrophilic structural unit in copolymerization component, and side chain hangs polyether-based, comprises esterification branched polyether and ammonia esterification branched polyether, object lesson following (being not limited only to this):
The weight portion of copolymerization units in water soluble thermo-crosslinked copolymer containing branched polyether hydrophilic-structure is 10-30 part.
Synthesize the method that water soluble thermo-crosslinked copolymer of the present invention adopts solution or emulsion copolymerization, the optional random copolymerization of copolyreaction or block copolymerization, preferred random copolymerization.The initator of polymerization comprises peroxide as di-tert-butyl peroxide, benzoyl peroxide, and persulfate is as potassium peroxydisulfate, Ammonium Persulfate 98.5, and azo-compound is as azodiisobutyronitrile etc., and copolymerization mode preferred solution is polymerized.
Available reaction dissolvent has water, methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, butanols, acetone, MEK, cyclohexanone, ethyl acetate, butyl acetate, oxolane, 1, 4-dioxane, N, dinethylformamide, dimethylacetylamide acetone, methyl ethyl ketone, cyclohexane, ethylene dichloride, toluene, EGME, ethylene glycol ethyl ether, glycol dimethyl ether, propylene glycol monomethyl ether, propylene-glycol ethyl ether, acetylacetone,2,4-pentanedione, DAA, ethylene glycol monomethyl ether acetate, ethyl cellosolve acetate, glycol isopropyl ether, butyl glycol ether acetic acid esters, 3-methoxypropanol, methoxymethoxy ethanol, diethylene glycol dimethyl ether, diethylene glycol ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol methyl ether acetate, propylene-glycol ethyl ether acetic acid esters, , methyl-sulfoxide, methyl lactate and ethyl lactate etc., or their mixture.The preferred 40-100 DEG C of copolyreaction temperature, optimum is 60-90 DEG C.
Water soluble thermo-crosslinked copolymer weight average molecular weight of the present invention is 40000-10000.Glass transition temperature is 110-130 DEG C.
The weight portion of the water soluble thermo-crosslinked copolymer of the present invention's design is 30-70 part, is preferably 40-60 part.
The present invention is by adding the water development of the performed polymer raising plate containing hydrophilic group.LASER HEAT energy passes through infrared light radiation absorbing dye by energy trasfer to cationic initiator, and cationic initiator produces homolysis, and the free radical of generation makes the performed polymer and the polyfunctional monomer generation radical polymerization that contain hydrophilic group, realizes free radical thermographic.Performed polymer containing hydrophilic group has a lot, as polyether-based acrylic compounds performed polymer, amide groups acrylic compounds performed polymer, sulfoamido acrylic compounds performed polymer, lactone acrylic compounds performed polymer and polyurethanes performed polymer etc.Performed polymer containing hydrophilic group of the present invention has following structure:
It has a little several: 1, containing polyurethane-base-NHCOO, and after radical polymerization, heat-sensitive layer has the characteristic of polyurethane as the advantage of pliability, solvent resistance, wearability; 2, the pi-allyl containing the high spatial free degree, activity is higher; 3, the carboxyl base containing the high spatial free degree, hydrophily is better; 4, class bis-phenol structure, after polymerization, rete rigidity is better, improves wearability.
Weight portion containing the performed polymer of hydrophilic group is 10-50 part, is preferably 20-40 part.
The present invention contains two kinds of hydrophily functional compounds, water soluble thermo-crosslinked copolymer contains esterification and hangs polyether-based, and the performed polymer containing hydrophilic group contains bis-phenol structure carboxyl, and these two kinds of hydrophilic groups all have very high space stretching, there is very strong hydrophily, improve the water development ability of plate.
Described polyfunctional monomer is polyfunctional group acrylic monomer or polyfunctional group polyurethane acroleic acid class monomer.The plate that radical polymerization can occur can use various types of monomer, as: Monofunctional monomers, has (methyl) acrylate as ethyl acrylate, butyl acrylate, allyl acrylate etc.; Polyfunctional monomer, there is diacrylate, 1,6-hexanediyl ester, pentaerythritol triacrylate and tetraacrylate, 1,3,5-tri--(2-acrylyl oxy-ethyl) isocyanuric acid ester, hydroxypropyl glycerine base triacrylate, ethoxy trimethylolpropane triacrylate, polyethylene glycol dimethacrylate etc.; Isocyanate group monomer, has 2-methacryloyloxyethyl acetoacetic ester and dimethyl-m-isopropenyl benzyl isocyanate ester etc., preferably uses polyfunctional monomer.Polyfunctional monomer in heat-sensitive layer of the present invention is selected from polyfunctional group acrylic monomer or polyfunctional group polyurethane acroleic acid class monomer.The weight portion of polyfunctional monomer is 10 ~ 30 parts, preferably 15 ~ 20 parts.
Described cationic initiator is salt compounded of iodine, the one of sulfosalt or at least two kinds; Cationic initiator heat decomposition temperature is 150-200 DEG C.Salt compounded of iodine, sulfosalt can mix with arbitrary proportion.Sheet material has dual imaging capability, can realize cationic crosslinked and radical polymerization.LASER HEAT energy passes through infrared light radiation absorbing dye by energy trasfer to cationic initiator, cationic initiator produces heterolytic fission and homolysis, heterolytic fission releases cation, make the epoxy radicals cross-linked polymeric in water soluble thermo-crosslinked copolymer, the free radical that homolysis produces simultaneously makes the performed polymer and the polyfunctional monomer generation radical polymerization that contain hydrophilic group, realize dual thermographic, be cross-linked with single epoxy radicals or compared with radical polymerization, improve plate pressrun.Cationic initiator of the present invention is selected from salt, as sulfosalt, salt compounded of iodine etc.Suitable salt comprises sulfosalt, the sub-maple salt of oxygen, oxygen sulfonium salt, sulfoxide salt, diazol and halogen as iodine anchor salt etc.The instantiation of the salt be applicable to is as: chlorinated diphenyl base salt compounded of iodine, hexafluorophosphoric acid diphenyl iodnium, hexafluoro-antimonic acid diphenyl iodnium, hexafluoro-antimonic acid [4-[(2-hydroxy-tetradecyl base-oxygen base] phenyl] phenyl salt compounded of iodine, tetrafluoro boric acid triphenylsulfonium salt compounded of iodine, octyl sulfate triphenylsulfonium salt compounded of iodine, hexafluorophosphoric acid-2-methoxyl group-4-aminophenyl diazonium salt, hexafluoro-antimonic acid Phenoxyphenyl diazol etc.Cationic initiator of the present invention be selected from can there is homolysis and heterolytic fission simultaneously salt compounded of iodine, sulfosalt one or more.Its heat decomposition temperature is at 150-200 DEG C.The weight portion of cationic initiator is 1 ~ 20 part, preferably 5 ~ 15 parts.
Described infrared light radiation absorbing dye is the cyanine dyes of absworption peak at 750-850nm.Component infrared light radiation absorbing dye in heat-sensitive layer of the present invention mainly plays energy trasfer, laser energy is passed to cationic initiator by infrared light radiation absorbing dye by the heat of infrared laser, cationic initiator produces heterolytic fission and homolysis, heterolytic fission releases cation, make the epoxy radicals cross-linked polymeric in water soluble thermo-crosslinked copolymer, the free radical that homolysis produces simultaneously makes the performed polymer and the polyfunctional monomer generation radical polymerization that contain hydrophilic group, realize dual thermographic, be cross-linked with single epoxy radicals or compared with radical polymerization, improve plate pressrun.
Maximum absorption wavelength scope containing infrared absorbing compounds in temperature-sensitive version heat-sensitive layer is 750-1100nm, is selected from carbon black, azo dyes, triaryl amine dyestuff, indoline dye, oxonol dye, cyanine dye, merocyanine dye, indole cyanine dyes, phthalocyanine dye, polythiophene dye, pyrazoline azo dye, oxazine dye, naphthoquinone dyestuff, anthraquinone dye, quinoneimine dye, methine dyes, porphyrin dye etc.Component contained by negative graph photosensitive composition of the present invention: infrared light radiation absorbing dye is the cyanine dyes that absorption maximum ranges preferably from 750-850nm, the weight portion of infrared light radiation absorbing dye is 1 ~ 20 part, preferably 5 ~ 15 parts.
Described heat-sensitive layer coating dry weight is 8-15mg/dm2, and described protective layer dry weight is 5-20mg/dm2.
Aqueous developable exempts from a preparation method for chemical treatment temperature-sensitive version, it is characterized in that: it comprises the following steps: (1) process aluminum substrate support; (2) coated heat photosensitive layer on aluminum substrate support after treatment; (3) coat protective layer on heat-sensitive layer.
Described process aluminum substrate support comprises the electrolyzing and coarsening of aluminum substrate support and anodic oxidation and the sealing pores that carries out, and after process, aluminum substrate support center line average boldness is 0.4-0.6 μm.
Heat-sensitive layer composition of the present invention need be applied on temperature-sensitive plate support, and the support of temperature-sensitive version comprises paper mold base, polyester-based, flexographic base, composite version base and metallograph base as copperplate base, aluminum substrate etc.Temperature-sensitive plate support selected by the present invention is aluminum substrate, a kind of aluminum substrate through special process process.
Aluminum substrate treatment process: the present invention's version base used is through electrolyzing and coarsening and anodic oxidation and aluminum substrate after carrying out sealing pores, and its center line average boldness is at 0.4-0.6um.Such version base obtains by the method for various electrolyzing and coarsening.Aluminum substrate of the present invention is high-purity aluminium plate, and its aluminium content is preferably more than 99%.Suitable aluminum substrate is (but being not limited only to this): iron accounts for 0.1%-0.5%, silicon accounts for 0.03%-0.3%, copper accounts for 0.003%-0.03%, and titanium accounts for 0.01%-0.l%.Electrolyzing and coarsening electrolyte used can be acid, alkali or the aqueous solution of salt or the aqueous solution containing organic solvent.Wherein, electrolyte is made with the aqueous solution of hydrochloric acid, nitric acid or their salt better.First aluminium plate is placed in the aqueous solution of NaOH, potassium hydroxide, sodium carbonate, sodium metasilicate etc. of 1%-30%, at the temperature of 20-80 DEG C, carries out the chemical attack of 5-250 second.Then in the nitric acid or sulfuric acid of 10%-30% with the temperature of 20-70 DEG C in and, to remove grey matter.Like this through the aluminium plate of cleaning, at the temperature of 10-6O DEG C, with square wave, the bench-type ripple or sine wave etc. of positive and negative sexual intercourse change, with 5-100A/dm
2current density, electrolytic treatments 10-300 second in the electrolyte of nitric acid or hydrochloric acid.Then, the aluminium plate through electrolysis carries out anodized.Anodic oxidation uses sulfuric acid process usually.The concentration of the sulfuric acid used is 5-30%, and current density is 1-15A/dm
2, oxidizing temperature is at 20-60 DEG C, and oxidization time is 5-250 second, to form 1-10g/m
2oxide-film.The oxide-film of such formation has higher oxide-film micropore usually, and adsorption capacity is comparatively strong, is easy to adhere to foul.So usually also need to carry out sealing pores.Sealing pores can use various method, is good to reach the 50-80% volume of closed oxide-film micropore.Last on the aluminium sheet through above-mentioned process, coating PVPA, thickness is 3mg/m2.
Heat-sensitive layer composition of the present invention can also comprise the auxiliary agent of some other necessity, as institute's solvent, normal temperature thermal polymerization inhibitor, coating colours, surfactant etc.
Solvent is mainly in order to prepare the photosensitive liquid of heat-sensitive layer, the photosensitive liquid solvent of preparation heat-sensitive layer comprises: acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, oxolane, toluene, EGME, ethylene glycol ethyl ether, glycol dimethyl ether, propylene glycol monomethyl ether, propylene-glycol ethyl ether, acetylacetone,2,4-pentanedione, cyclohexanone, DAA, ethylene glycol monomethyl ether acetate, ethyl cellosolve acetate, glycol isopropyl ether, butyl glycol ether acetic acid esters, 3-methoxypropanol, methoxymethoxy ethanol, diethylene glycol dimethyl ether, diethylene glycol ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol methyl ether acetate, propylene-glycol ethyl ether acetic acid esters, N.N-dimethyl formamide, methyl-sulfoxide, methyl lactate and ethyl lactate etc.Solvent can use with pure material form or form of mixtures.
Normal temperature thermal polymerization inhibitor is to prevent sheet material to be polymerized at normal temperatures, improves the ordinary temperature stability of plate.Thermal polymerization inhibitor comprises: quinhydrones, NO free radical piperidine alcohols, p methoxy phenol, BHT, 1,2,3,-thrihydroxy-benzene, tert-butyl catechol, benzoquinones, 4,4 '-thiobis-(3 methy 6 tert butyl phenol), 2,2 '-di-2-ethylhexylphosphine oxide (4-methyl isophthalic acid 6-tert-butyl phenol), and uncle's cerium salt of N-nitroso phenylhydroxylamine etc.
Heat-sensitive layer contains layer colouring agent.In order to increase the image density after the plate-making of temperature-sensitive version, being convenient to carry out visual inspection or graphical analysis measurement device measurement plate performance to temperature-sensitive version after plate-making, in the temperature-sensitive layer of temperature-sensitive version of the present invention, adding layer colouring agent.It comprises: crystal violet, ethyl violet, crystal violet, purple in crystallization, Victoria blue, glossy dark green, oil blue, oil yellow, rhodamine B, crystal violet rowland, malachite green, methylene blue, triazines etc.
Heat-sensitive layer contains surfactant, can select non-ionic surface active agent, amphoteric surfactant, silicon-containing surfactant, fluorine-containing surfactant etc.As betaines, tristerin class, sorbic acid palm fibre grease class, polysiloxane-based, poly-fluoroalkyl ethers.
As temperature-sensitive version of the present invention, heat-sensitive layer is coated with layer protective layer, prevents the performance of the pollutant effect heat-sensitive layer in the oxygen that exists in air or other environment.As the material for the protection of layer, the water miscible polymer of preferred tool, as poly-(vinyl alcohol), polyvinylpyrrolidone, acid cellulose derivative, gelatin, gum arabic and poly-(allyl phenol etc.These materials can obtain as the main component of protective layer and refuse oxygen and development removeability very well.For the object lesson of polyvinyl alcohol, can be exemplified as 71-100% hydrolysis and molecular weight is the compound of 300-2400.Object lesson has: PVA-105, PVA-110, PVA-117, PVA-117H.PVA-120, PVA-124.PVA-124H.PVA-CS.PVA-CST, PVA-HC.PVA-203, PVA-204, PVA-205, PVA-210, PVA-217, PVA-220, PVA-224, PVA-217EE, PVA-217E, PVA-220E.PVA-224E, PVA-405, PVA-420, PVA-613 etc.The coating weight of protective layer is generally 5-20mg/dm in dry mass
2, be preferably 10-15mg/dm
2
Usually with this field, oneself knows that technology coating (e.g., cutter is coated with, blade coating, and bar is coated with, roller coat, extrusion etc.) is on aluminum substrate to heat-sensitive composition of the present invention.
Below in conjunction with specific embodiment, the present invention is described in detail:
Raw material can obtain from following company: styrene St: Han Dynasty in Shandong Province honor Energy Science Co., Ltd; Methacrylonitrile MAN, acrylonitrile AN: Tianjin chemical reagent two factory; C1, C2, C3, C4 example compound: Mitsubishi chemistry; Different polymerization degree example compound D1, D2, D3, D4: SIGMA company of Britain; MEK MEK: Japan improves petrochemical industry.Azo-bis-isobutyl cyanide: the gloomy chemistry of good fortune; Benzoyl peroxide BPO: Laiwu health novel agent.
Part I: water soluble thermo-crosslinked copolymer (code name P) synthesizes example P01-P10
Embodiment (1) (water soluble thermo-crosslinked copolymer p 01)
Be with at 1000ml in the four-hole boiling flask of temperature control heating, mechanical agitation, condensing reflux and nitrogen protection device and add 333.3g MEK, 10g,(10 % by weight) example compound D2 (n about 60); heating stirs; 70g,(70 % by weight is dripped at 90 DEG C) St (styrene), 10g (10 % by weight) AN (acrylonitrile), 10g,(10 % by weight) example compound C2; 0.7g benzoyl peroxide BPO; time for adding 20 minutes; 0.3g benzoyl peroxide BPO is added after reacting 7.5 hours again; continue to react after 12 hours again and terminate, performance sees attached list 1.
Embodiment (2) (water soluble thermo-crosslinked copolymer p 02)
Temperature control heating is with at 1000ml, mechanical agitation, 344.8g MEK is added in the four-hole boiling flask of condensing reflux and nitrogen protection device, 10g(10 % by weight) example compound D4 (n about 50), heating stirs, 60g,(60 % by weight is dripped at 80 DEG C) St (styrene), 20g (20 % by weight) AN (acrylonitrile), 10g(10 % by weight) example compound C3, 0.7gAIBN (azodiisobutyronitrile), time for adding 20 minutes, 0.3gAIBN (azodiisobutyronitrile) is added after reacting 7.5 hours again, continue to react again after 12 hours and terminate, performance sees attached list 1.
Embodiment (3) (water soluble thermo-crosslinked copolymer p 03)
Temperature control heating is with at 1000ml, mechanical agitation, 384.6g MEK is added in the four-hole boiling flask of condensing reflux and nitrogen protection device, 10g(10 % by weight) example compound D4 (n about 40), heating stirs, 50g,(50 % by weight is dripped at 80 DEG C) St (styrene), 30g (30 % by weight) AN (acrylonitrile), 10g(10 % by weight) example compound C2, 0.7gAIBN (azodiisobutyronitrile), time for adding 20 minutes, 0.3gAIBN (azodiisobutyronitrile) is added after reacting 7.5 hours again, continue to react again after 12 hours and terminate, performance sees attached list 1.
Embodiment (4) (water soluble thermo-crosslinked copolymer p 04)
Temperature control heating is with at 1000ml, mechanical agitation, 416.7g MEK is added in the four-hole boiling flask of condensing reflux and nitrogen protection device, 30g(30 % by weight) example compound D2 (n about 20), heating stirs, 40g,(40 % by weight is dripped at 80 DEG C) St (styrene), 10g (10 % by weight) AN (acrylonitrile), 20g(20 % by weight) example compound C3, 0.7gAIBN (azodiisobutyronitrile), time for adding 20 minutes, 0.3gAIBN (azodiisobutyronitrile) is added after reacting 7.5 hours again, continue to react again after 12 hours and terminate, performance sees attached list 1.
Embodiment (5) (water soluble thermo-crosslinked copolymer p 05)
Temperature control heating is with at 1000ml, mechanical agitation, 454.5g MEK is added in the four-hole boiling flask of condensing reflux and nitrogen protection device, 10g(10 % by weight) example compound D2 (n about 50), heating stirs, 60g,(60 % by weight is dripped at 80 DEG C) St (styrene), 10g (10 % by weight) AN (acrylonitrile), 20g(20 % by weight) example compound C2, 0.7gAIBN (azodiisobutyronitrile), time for adding 20 minutes, 0.3gAIBN (azodiisobutyronitrile) is added after reacting 7.5 hours again, continue to react again after 12 hours and terminate, performance sees attached list 1.
Embodiment (6) (water soluble thermo-crosslinked copolymer p 06)
Temperature control heating is with at 1000ml, mechanical agitation, 500g MEK is added in the four-hole boiling flask of condensing reflux and nitrogen protection device, 10g(10 % by weight) example compound D4 (n about 40), heating stirs, 50g,(50 % by weight is dripped at 80 DEG C) St (styrene), 10g (10 % by weight) AN (acrylonitrile), 30g(30 % by weight) example compound C3, 0.7g AIBN (azodiisobutyronitrile), time for adding 20 minutes, 0.3gAIBN (azodiisobutyronitrile) is added after reacting 7.5 hours again, continue to react again after 12 hours and terminate, performance sees attached list 1.
Embodiment (7) (water soluble thermo-crosslinked copolymer p 07)
Temperature control heating is with at 1000ml, mechanical agitation, 555.5g MEK is added in the four-hole boiling flask of condensing reflux and nitrogen protection device, 30g(30 % by weight) example compound D4 (n about 20), heating stirs, 40g,(40 % by weight is dripped at 80 DEG C) St (styrene), 20g (20 % by weight) AN (acrylonitrile), 10g(10 % by weight) example compound C2, 0.7g AIBN (azodiisobutyronitrile), time for adding 20 minutes, 0.3g AIBN (azodiisobutyronitrile) is added after reacting 7.5 hours again, continue to react again after 12 hours and terminate, performance sees attached list 1.
Embodiment (8) (water soluble thermo-crosslinked copolymer p 08)
Temperature control heating is with at 1000ml, mechanical agitation, 588.2g MEK is added in the four-hole boiling flask of condensing reflux and nitrogen protection device, 20g(20 % by weight) example compound D2 (n about 30), heating stirs, 60g,(60 % by weight is dripped at 80 DEG C) St (styrene), 10g (10 % by weight) AN (acrylonitrile), 10g(10 % by weight) example compound C3, 0.7g AIBN (azodiisobutyronitrile), time for adding 20 minutes, 0.3gAIBN (azodiisobutyronitrile) is added after reacting 7.5 hours again, continue to react again after 12 hours and terminate, performance sees attached list 1.
Embodiment (9) (water soluble thermo-crosslinked copolymer p 09)
Temperature control heating is with at 1000ml, mechanical agitation, 769.2g MEK is added in the four-hole boiling flask of condensing reflux and nitrogen protection device, 30g(30 % by weight) example compound D1 (n about 30), heating stirs, 50g,(50 % by weight is dripped at 70 DEG C) St (styrene), 10g (10 % by weight) MAN (methacrylonitrile), 10g(10 % by weight) example compound C1, 0.7g AIBN (azodiisobutyronitrile), time for adding 20 minutes, 0.3g AIBN (azodiisobutyronitrile) is added after reacting 7.5 hours again, continue to react again after 12 hours and terminate, performance sees attached list 1.
Embodiment (10) (water soluble thermo-crosslinked copolymer p 10)
Temperature control heating is with at 1500ml, mechanical agitation, 1000g MEK is added in the four-hole boiling flask of condensing reflux and nitrogen protection device, 10g(10 % by weight) example compound D3 (n about 60), heating stirs, 40g,(40 % by weight is dripped at 60 DEG C) St (styrene), 30g (30 % by weight) MAN (methacrylonitrile), 20g(20 % by weight) example compound C4, 0.7g AIBN (azodiisobutyronitrile), time for adding 20 minutes, 0.3g AIBN (azodiisobutyronitrile) is added after reacting 7.5 hours again, continue to react again after 12 hours and terminate, performance sees attached list 1.
Comparative example 1-5(synthesizes similar Ai Kefa polymer A 1-A5):
Introduces according to Ai Kefa patent EP 2006-5-24 06114475.4, send out the similar Ai Kefa polymer of synthesis with polymerisation in solution, but polymer is not containing hydrophilic radical, polymer architecture:
Basic operation: be with at 1000ml in the four-hole boiling flask of temperature control heating, mechanical agitation, condensing reflux and nitrogen protection device and add 400 MEKs, 5g lauryl sodium sulfate; 60g,(60 % by weight is dripped at 80 DEG C) ST (styrene), 40g (40 % by weight) AN (acrylonitrile), 0.7g AIBN (azodiisobutyronitrile); time for adding 0.5 hour; add 0.3gAIBN (azodiisobutyronitrile) after reacting 7.5 hours again, continue to react again after 12 hours and terminate.
Change charge ratio, reaction density, synthesize similar Ai Kefa polymer A 1-A5, performance sees attached list 1.
Comparative example 6-10(synthesizes similar Kodak polymer K1-K5):
According to Kodak patent US 2005-8-3 11/196, send out the similar Ai Kefa polymer of synthesis with polymerisation in solution, polymer containing changing hydrophilic radical, but does not contain epoxy radicals, polymer architecture:
Basic operation: 1000ml be with temperature control heating, mechanical agitation, condensing reflux and nitrogen protection device four-hole boiling flask in add 400g MEK; drip 20,g(0 % by weight at 80 DEG C) ST (styrene), 70g (70 % by weight) AN (acrylonitrile), 20g0.7g (20 % by weight) PEGMA (polyethoxy methacrylate), AIBN (azodiisobutyronitrile); time for adding 0.5 hour; add 0.3g AIBN (azodiisobutyronitrile) after reacting 7.5 hours again, continue to react again after 12 hours and terminate.
Change charge ratio, reaction density, synthesize similar Kodak polymer K1-K5, performance sees attached list 1.
Part II: the synthesis containing the performed polymer (code name M) of hydrophilic group:
Intermediate k1 (purchased from Ai Kefa speciality chemical company, commercial disignation v003554):
Intermediate k2(is purchased from Japanese Showa electrician SDK, commercial disignation Karenz MOI):
MEK MEK: Japan improves petrochemical industry.
Dibutyl tin laurate: Tianjin chemical reagent one factory.
Be with at 2000ml in the four-hole boiling flask of temperature control heating, mechanical agitation, condensing reflux and nitrogen protection device and add 288.0g intermediate k1,150g MEK MEK, 6.0g dibutyl tin laurate; nitrogen protection; be heated to 60 DEG C of 310.0g intermediate k2 dripped; time for adding 30 minutes; react 2 hours; react 48 hours under ice-water bath, until disappeared by peak, infrared spectrum detection of active NCO 2275 place, obtain the MEK solution that solid content is the target compound M of 80%.
Be below exemplifying embodiment of the present invention, but be not limited to following instance:
Embodiment 1
The preparation of version base: the A1050 of purity 99.5%, thick 0.3mm rolls aluminium plate, in the sodium hydrate aqueous solution of 5%, etch 20 seconds at 70 DEG C, after running water, neutralizes with the aqueous solution of nitric acid of 1% immediately.Then in the aqueous hydrochloric acid solution of 1%, at 40 DEG C with sine wave alternating current with the current density electrolysis alligatoring 16 seconds of 50A/dm2.Then at 40 DEG C, with in the sodium hydrate aqueous solution of 5% and 10 seconds.Washing.Last at 30 DEG C, with the aqueous sulfuric acid of 20%, with the current density of 15A/dm2, anodic oxidation 20 seconds.Washing.Sealing pores is carried out 18 seconds with the sodium silicate aqueous solution of 5% at 80 DEG C.Washing.Dry.The version base obtained like this, center line average boldness is 0.5um, the heavy 3.0g/dm2 of oxide-film.
Heat-sensitive layer is coated with: at above-mentioned photosensitive liquid on the version base of hydrophilicity-imparting treatment below extrusion coated, then at 100 DEG C dry 60 seconds.Obtain the dry coating weight of 10mg/dm2.Photosensitive liquid uses component (each component is by weight) below:
Protective layer is coated with: the protective layer solution that extrusion coated is following on heat-sensitive layer obtained above, then at 110 DEG C dry 60 seconds.Obtain the dry coating weight (each component by weight) of 10mg/dm2.
The structure of infrared absorbing dye ADS830 is as follows:
The plate obtained like this in the all-victorious thermosensitive CTP platemaking machine of Kodak with 120mJ/cm
2energy expose.Its performance is listed in table 2 below.
Embodiment 2
Version base, heat-sensitive layer and protective layer is prepared above by identical method.Photosensitive liquid component the following:
The plate obtained like this in the all-victorious thermosensitive CTP platemaking machine of Kodak with 120mJ/cm
2energy expose.Its performance is listed in table 2 below.
Embodiment 3
Version base, heat-sensitive layer and protective layer is prepared above by identical method.Photosensitive liquid component the following:
The plate obtained like this in the all-victorious thermosensitive CTP platemaking machine of Kodak with 120mJ/cm
2energy expose.Its performance is listed in table 2 below.
Embodiment 4
Version base, heat-sensitive layer and protective layer is prepared above by identical method.Photosensitive liquid component the following:
The plate obtained like this in the all-victorious thermosensitive CTP platemaking machine of Kodak with 120mJ/cm
2energy expose.Its performance is listed in table 2 below.
Embodiment 5
Version base, heat-sensitive layer and protective layer is prepared above by identical method.Photosensitive liquid component the following:
The plate obtained like this in the all-victorious thermosensitive CTP platemaking machine of Kodak with 120mJ/cm
2energy expose.Its performance is listed in table 2 below.
Embodiment 6
Version base, heat-sensitive layer and protective layer is prepared above by identical method.Photosensitive liquid component the following:
The plate obtained like this in the all-victorious thermosensitive CTP platemaking machine of Kodak with 120mJ/cm
2energy expose.Its performance is listed in table 2 below.
Embodiment 7
Version base, heat-sensitive layer and protective layer is prepared above by identical method.Photosensitive liquid component the following:
The plate obtained like this in the all-victorious thermosensitive CTP platemaking machine of Kodak with 120mJ/cm
2energy expose.Its performance is listed in table 2 below.
Embodiment 8
Version base, heat-sensitive layer and protective layer is prepared above by identical method.Photosensitive liquid component the following:
The plate obtained like this in the all-victorious thermosensitive CTP platemaking machine of Kodak with 120mJ/cm
2energy expose.Its performance is listed in table 2 below.
Embodiment 9
Version base, heat-sensitive layer and protective layer is prepared above by identical method.Photosensitive liquid component the following:
The plate obtained like this in the all-victorious thermosensitive CTP platemaking machine of Kodak with 120mJ/cm
2energy expose.Its performance is listed in table 2 below.
Embodiment 10
Version base, heat-sensitive layer and protective layer is prepared above by identical method.Photosensitive liquid component the following:
The plate obtained like this in the all-victorious thermosensitive CTP platemaking machine of Kodak with 120mJ/cm
2energy expose.Its performance is listed in table 2 below.
Embodiment 11
Version base, heat-sensitive layer and protective layer is prepared above by identical method.Photosensitive liquid component the following:
The plate obtained like this in the all-victorious thermosensitive CTP platemaking machine of Kodak with 120mJ/cm
2energy expose.Its performance is listed in table 2 below.
Embodiment 12
Version base, heat-sensitive layer and protective layer is prepared above by identical method.Photosensitive liquid component the following:
The plate obtained like this in the all-victorious thermosensitive CTP platemaking machine of Kodak with 120mJ/cm
2energy expose.Its performance is listed in table 2 below.
Embodiment 13
Version base, heat-sensitive layer and protective layer is prepared above by identical method.Photosensitive liquid component the following:
The plate obtained like this in the all-victorious thermosensitive CTP platemaking machine of Kodak with 120mJ/cm
2energy expose.Its performance is listed in table 2 below.
Embodiment 14
Version base, heat-sensitive layer and protective layer is prepared by the method that embodiment 1 is identical.The center line average boldness of edition base is just made to be 0.4um
The plate obtained like this in the all-victorious thermosensitive CTP platemaking machine of Kodak with 120mJ/cm
2energy expose.Its performance is listed in table 2 below.
Embodiment 15
Version base, heat-sensitive layer and protective layer is prepared by the method that embodiment 1 is identical.The center line average boldness of edition base is just made to be 0.6um
The plate obtained like this in the all-victorious thermosensitive CTP platemaking machine of Kodak with 120mJ/cm
2energy expose.Its performance is listed in table 2 below.
Embodiment 16
Version base, heat-sensitive layer and protective layer is prepared by the method that embodiment 1 is identical.The dry coating of heat-sensitive layer is just made to be heavily 8mg/dm
2
The plate obtained like this in the all-victorious thermosensitive CTP platemaking machine of Kodak with 120mJ/cm
2energy expose.Its performance is listed in table 2 below.
Embodiment 17
Version base, heat-sensitive layer and protective layer is prepared by the method that embodiment 1 is identical.The dry coat weight of heat-sensitive layer is just made to be 15mg/dm2
The plate obtained like this in the all-victorious thermosensitive CTP platemaking machine of Kodak with 120mJ/cm
2energy expose.Performance is listed in table 2 below.
Embodiment 18
Version base, heat-sensitive layer and protective layer is prepared by the method that embodiment 1 is identical.The dry coat weight of protective layer is just made to be 5mg/dm
2
The plate obtained like this in the all-victorious thermosensitive CTP platemaking machine of Kodak with 120mJ/cm
2energy expose.Its performance is listed in table 2 below.
Embodiment 19
Version base, heat-sensitive layer and protective layer is prepared by the method that embodiment 1 is identical.The dry coat weight of protective layer is just made to be 20mg/dm
2
The plate obtained like this in the all-victorious thermosensitive CTP platemaking machine of Kodak with 120mJ/cm
2energy expose.Its performance is listed in table 2 below.
Wherein, the water-soluble polymer P1-P10 of embodiment 1-19 is water soluble thermo-crosslinked copolymer, M is the performed polymer containing hydrophilic group, pentaerythritol triacrylate is polyfunctional monomer, diaryl hexafluorophosphoric acid salt compounded of iodine is cationic initiator, and infrared light radiation absorbing dye ADS830 is infrared light radiation absorbing dye, NO free radical piperidine alcohols normal temperature thermal polymerization inhibitor, alkaline bright blue is layer colouring agent, and MEK and 1-methoxy-2-propanol are solvent.
Comparative example 1-5
Version base, heat-sensitive layer and protective layer is prepared by the method that embodiment 1 is identical.Photosensitive coating fluid uses component below:
The plate obtained like this in the all-victorious thermosensitive CTP platemaking machine of Kodak with 120mJ/cm
2energy expose.Its performance is listed in table 2 below.
Comparative example 6-10
Version base, heat-sensitive layer and protective layer is prepared by the method that embodiment 1 is identical.Photosensitive coating fluid uses component below:
The plate obtained like this in the all-victorious thermosensitive CTP platemaking machine of Kodak with 120mJ/cm
2energy expose, plate performance sees attached list 2.
Shown by the detection application result of subordinate list, compared with radical polymerization mechanism plate, the aqueous developable of the present invention's design is exempted from chemical treatment temperature-sensitive version and is had dual imaging capability, can realize cationic crosslinked and radical polymerization, improve imaging capability and the pressrun of plate; Performed polymer containing hydrophilic group contains polyurethane-base-NHCOO, and rete has the advantage of pliability, solvent resistance, wearability; Pi-allyl containing the high spatial free degree, activity is higher, and site reduction is better; Plate contains two kinds of hydrophilic row functional compounds, water soluble thermo-crosslinked copolymer contains esterification and hangs polyether-based, performed polymer containing hydrophilic group contains bis-phenol structure carboxyl, these two kinds of hydrophilic groups all have very high space stretching, there is very strong hydrophily, improve the water development ability of plate, the water development of environmental protection can be realized.
Subordinate list 1: polymer performance table
Subordinate list 2: plate application performance table
Claims (9)
1. an aqueous developable exempts from chemical treatment temperature-sensitive version; it is characterized in that: it comprises support, heat-sensitive layer and protective layer, described heat-sensitive layer comprises the raw material of following weight parts meter: water soluble thermo-crosslinked copolymer 30-70 part, the performed polymer 10-50 part containing hydrophilic group, polyfunctional monomer 10-30 part, cationic initiator 1-20 part, infrared light radiation absorbing dye 1-20 part.
2. aqueous developable according to claim 1 exempts from chemical treatment temperature-sensitive version, it is characterized in that: described heat-sensitive layer comprises the raw material of following weight parts meter: water soluble thermo-crosslinked copolymer 40-60 part, the performed polymer 20-40 part containing hydrophilic group, polyfunctional monomer 15-20 part, cationic initiator 5-15 part, infrared light radiation absorbing dye 5-15 part.
3. aqueous developable according to claim 1 and 2 exempts from chemical treatment temperature-sensitive version, it is characterized in that: described water soluble thermo-crosslinked copolymer has following structure:
Wherein, R1, R2, R4 are H atom or methyl; R3 is
or
; R5 is O atom or OCH2CH2NHCOO, n is the integer of 20-60; A, b, c, d are the weight portion of corresponding copolymerization units, and weight portion shared by a is 40-70 part, and weight portion shared by b is 10-30 part, and weight portion shared by c is 10-30 part, and weight portion shared by d is 10-30 part.
4. aqueous developable according to claim 1 and 2 exempts from chemical treatment temperature-sensitive version, it is characterized in that: the described performed polymer containing hydrophilic group has following structure:
Aqueous developable according to claim 1 and 2 exempts from chemical treatment temperature-sensitive version, it is characterized in that: described polyfunctional monomer is polyfunctional group acrylic monomer or polyfunctional group polyurethane acroleic acid class monomer.
5. aqueous developable according to claim 1 and 2 exempts from chemical treatment temperature-sensitive version, it is characterized in that: described cationic initiator is salt compounded of iodine, the one of sulfosalt or at least two kinds; Cationic initiator heat decomposition temperature is 150-200 DEG C
.
6. aqueous developable according to claim 6 exempts from chemical treatment temperature-sensitive version, it is characterized in that: described infrared light radiation absorbing dye is the cyanine dyes of absworption peak at 750-850nm.
7. aqueous developable according to claim 1 exempts from chemical treatment temperature-sensitive version, it is characterized in that: described heat-sensitive layer coating dry weight is 8-15mg/dm
2, described protective layer dry weight is 5-20mg/dm
2.
8. aqueous developable exempts from a preparation method for chemical treatment temperature-sensitive version, it is characterized in that: it comprises the following steps: (1) process aluminum substrate support; (2) coated heat photosensitive layer on aluminum substrate support after treatment; (3) coat protective layer on heat-sensitive layer.
9. aqueous developable according to claim 9 exempts from the preparation method of chemical treatment temperature-sensitive version, it is characterized in that: described process aluminum substrate support comprises the electrolyzing and coarsening of aluminum substrate support and anodic oxidation and the sealing pores that carries out, and after process, aluminum substrate support center line average boldness is 0. 4-0. 6 μm.
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| EP0980754B1 (en) * | 1998-08-14 | 2005-10-05 | Fuji Photo Film Co., Ltd. | Photopolymer composition, lithographic printing plate precursor and method of making lithographic printing plate |
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Effective date of registration: 20180212 Address after: 473003 Nanyang Station Road, Henan, No. 718 Co-patentee after: Beijing Aerospace innovation patent investment center (limited partnership) Patentee after: Lucky Huaguang Graphics Co., Ltd. Address before: 473003 Nanyang Station Road, Henan, No. 718 Patentee before: Lucky Huaguang Graphics Co., Ltd. |