CN102902161A - Negative image photosensitive composition and lithograph plate manufactured from same - Google Patents
Negative image photosensitive composition and lithograph plate manufactured from same Download PDFInfo
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- CN102902161A CN102902161A CN2012104261270A CN201210426127A CN102902161A CN 102902161 A CN102902161 A CN 102902161A CN 2012104261270 A CN2012104261270 A CN 2012104261270A CN 201210426127 A CN201210426127 A CN 201210426127A CN 102902161 A CN102902161 A CN 102902161A
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Abstract
The invention discloses a negative image photosensitive composition and a lithograph plate manufactured from the same. The negative image photosensitive composition comprises a water-soluble thermo-crosslinking copolymer with a branced chain containing color-variable groups, a photopolymerisable prepolymer, a polyfunctional monomer, a cation photopolymerization initiator and infrared radiation absorption dye, wherein in terms of weight percentage, the water-soluble thermo-crosslinking copolymer with the branced chain containing the color-variable groups accounts for 30-70% relative to the total amount of the solid composition, the photopolymerisable prepolymer accounts for 10-50% relative to the total amount of the solid composition, the polyfunctional monomer accounts for 10-30% relative to the total amount of the solid composition, the cation photopolymerization initiator accounts for 1-20% relative to the total amount of the solid composition, and the infrared radiation absorption dye accounts for 1-20% relative to the total amount of the solid composition. The photosensitive composition disclosed by the invention is suitable for preparing infrared-sensitive development-free CTP (Computer to Plate) lithograph plate. The lithograph plate disclosed by the invention is high in photosensitivity and good in lattice point reducibility, can be directly loaded on a machine for printing without any photographic processing procedures after being scanned and imaged by using infrared laser, is high in printing-down contrast after imaging and convenient for plate detection before loading, and achieves high pressrun.
Description
Technical field
The present invention relates to a kind of negative graph photosensitive composition, and a kind of flushing-free thermosensitive CTP sensitive lithographic plate.
Background technology
The preparation process of sensitive lithographic plate is known by the people in the industry in printing industry.The plate-making process of sensitive lithographic plate 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 therefrom an optical image latent image; The 2nd, the forme after the top exposure is carried out a so-called follow-up development step, by this process, remove unnecessary coating.Pre-coating sensitive lithographic is the flaky material take aluminium or polyester as support, and can make by above-mentioned two steps and have simultaneously oleophylic and hydrophilic surface, is suitable for lithography.Usually, in a negative-type system, the exposure position is because polymerization or crosslinked the changing of coating, becomes the insoluble or indissoluble of developer solution, thereby can in development step the coating at the unexposed position of forme be removed.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, usually develops in a processing unit that contains developer.The used developer of positive-type sensitive lithographic plate is highly basic normally, usually also contains organic solvent in the negative type developer solution except highly basic, such as phenmethylol etc.Certainly, also useful heating means or alternate manner are finished in the development of optical image.The shortcoming of above-mentioned two kinds (i.e. 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.
And along with the development of printing digitalization, it is like a raging fire that a kind of technology of the CTP of being known as plate also develops, this technology is to control as required the switching of CTP platemaking machine laser head by program software, then the digitized image of printing that needs is directly outputed on the precoating sensitive lithographic plate, make again the sensitive lithographic plate of the printing that is available on the machine by above-mentioned " developing process ".The CTP technology has realized the digitizing of plate making, and has saved the master production process, is undoubtedly a much progress of plate making, but this CTP plate-making technology needs one " developing process " equally, exists liquid waste processing and brings environmental problem.
For this blowdown and environmental issue, industry researchist has proposed various solutions.Be summed up the three kinds of modes that mainly contain:
A kind of is phase change technology by light sensitive layer, realizes that precoating planographic printing plate material surface oleophylic/hydrophilic polar changes, then directly locks up on the printing machine and print.This mode, oleophylic/hydrophilic realize there is not unnecessary coating shedding by light sensitive layer fully, have realized printing from making a plate to all the environmental protection purpose without emissions.But this mode exists that required plate-making energy is high, the printing ink balance easily changes and the low shortcoming of pressrun, therefore practical poor effect.
Another kind be exactly to the precoating sensitive lithographic plate by the scanning plate-making of CTP platemaking machine after, use " non-alkalescence or non-solvent " solution to carry out " pre-service ", removing the unnecessary coating in blank position, and then lock up printing machine printing.This mode, although the process of similar " wet developing " is arranged equally, employed but " pretreatment fluid " compares chemicals such as not had basic component and solvent with developer solution, the mechanism of removing the unnecessary coating in blank position is also fully different: the former is the physical process by the dissolving diffusion, and the latter but is that chemical reaction is main dissolving diffusion process.So this kind mode also claims " exempting from chemical treatment " technology.The advantage of this mode is both to have realized the relatively effect of environment protection emission, also can carry out the correction of site as conventional CTP plate before sensitive lithographic plate is printed on the machine simultaneously, in order to avoid become blind version on the sensitive lithographic plate behind the machine again.But there are some shortcomings too in this mode, that be exactly its " pretreatment fluid " be not pure water, but in water, added the chemicals such as some wetting agents, bleeding agent or Arabic gum, so fail to realize the environmental protection on the real significance.
Technology that another is so-called " processing at machine ", its principle is: the precoating planographic printing plate material is after making a plate by the scanning of CTP platemaking machine, its unnecessary coating that is used for the blank position of printing is to remove under the effect by damping water and printing ink on the printing machine, walked by the transferring paper tape behind the unnecessary coating removal, blank position is hydrophilic aluminum substrate, and this mode has realized the environmental protection purpose of plate-making process without emissions.But owing to directly being printed on the machine after such plate exposure, inconvenient image on the plate is carried out detection before the upper machine after as traditional CT P plate, developing with developing machine, therefore such plate need to the printing down contrast do larger, carry out image detection and to identify various look versions on locing up printing machine the time so that before locing up printing machine, detect, to prevent that the phenomenon of printing images mistake and wrongly installed look version position from occuring.
In order to improve the printing down contrast, various schemes have been proposed.International monopoly WO 2010/005488 Al has proposed a kind of method that improves the printing down contrast, in the top layer of plate, to contain the component that change color can occur under a kind of infrared light, this component can make plate produce the printing down contrast when plate-making, is conducive to image is detected.Its shortcoming is because the look change is the top layer generation on photographic layer, enters into photographic layer so the density that produces after look becomes can hinder light, thereby affect the photographic layer image taking speed.International monopoly WO 2010/033182 Al has disclosed a kind of method that improves the printing down contrast, be to have used a kind of Infrared dyes that can produce the special construction of change color under infrared light in photographic layer, this Infrared dyes can make plate produce the plate-making contrast when plate-making.But, because the use amount of Infrared dyes in the photographic layer solid constituent is limited, so the plate-making contrast that obtains is obvious not, be not enough to reach the requirement of detected image quality.Having disclosed a kind of method that improves the plate-making contrast among the European patent 1717024A1, is to add a kind of leuco dye in photographic layer, and this leuco dye is colourless before with infrared laser or ultraviolet exposure, then becomes coloured after the exposure.This method, the leuco dye consumption can not be too large, otherwise can have a strong impact on the plate imaging performance, so obtain the requirement that the printing down contrast of plate also is not enough to reach the detected image quality.
Summary of the invention
The object of the present invention is to provide a kind of infrared ray responsive exempt from the chemical treatment photosensitive composition and with the sensitive lithographic plate of its making, sensitive lithographic plate light sensitivity of the present invention is high, redeeming a vow to a god property of site is good, the printing down contrast is high after the imaging, be convenient to the front inspection version of machine, and can directly be printed on the machine without any need for the washing processing step, and can obtain high pressrun.
Purpose of the present invention can realize by following measures:
Negative graph photosensitive composition comprises the water soluble thermo-crosslinked multipolymer that side chain contains the changeable colour group, the performed polymer of photopolymerization, polyfunctional monomer, cationic photopolymerization initiating agent and infrared light radiation absorption dyestuff, by weight percentage, the water soluble thermo-crosslinked resin that side chain contains the changeable colour group accounts for the 30-70% of constituent solid amount, the performed polymer of photopolymerization accounts for the 10-50% of constituent solid amount, polyfunctional monomer accounts for the 10-30% of constituent solid amount, the cationic photopolymerization initiating agent accounts for the 1-20% of constituent solid amount, and infrared light radiation absorption dyestuff accounts for the 1-20% of constituent solid amount.
By weight percentage, the consumption of described water soluble thermo-crosslinked resin accounts for the 40-60% of constituent solid amount, the performed polymer of photopolymerization accounts for the 20-40% of constituent solid amount, polyfunctional monomer accounts for the 10-20% of constituent solid amount, the cationic photopolymerization initiating agent accounts for the 5-15% of constituent solid amount, and infrared light radiation absorption dyestuff accounts for the 5-15% of constituent solid amount.
Side chain contains the water soluble thermo-crosslinked multipolymer of changeable colour group, has following structure A:
R1, R2 are H atom or methyl, and R3 is CH
2=C (CH
3) the COOCH2CH2NCO-group, R4 is the groups such as amide group, ether (containing polyethoxy), pyrrolidone-base, X is the integer of 3-8.
M, n, o, p, q are the percent by weight of corresponding copolymerization units, and the m proportion is that 40 ~ 60%, n proportion is that 10 ~ 30%, o proportion is that 10 ~ 30%, p proportion is that 10 ~ 30%, q proportion is 10 ~ 30%.
The performed polymer of described photopolymerization is a kind of polyurethane acroleic acid class performed polymer.
Described polyfunctional monomer is selected from acrylic monomer, polyurethane acroleic acid class monomer or propylene oxide acid monomers.
Described cationic photopolymerization initiating agent is selected from one or more of salt compounded of iodine, sulfosalt, microcosmic salt, selenium salt.
The heat decomposition temperature of described cationic photopolymerization initiating agent is 150 ~ 200
oC.
Described infrared light radiation absorption dyestuff is a kind of water soluble cyanine that is absorbed in 780 ~ 850nm.
The sensitive lithographic plate that negative graph photosensitive composition of the present invention is made, it comprises: (1) aluminum substrate support, and (2) above-mentioned negative graph photosensitive composition coating layer, and (3) above-mentioned negative graph photosensitive composition coating layer is at protective seam the same side and on it.
The support of sensitive lithographic plate is through electrolyzing and coarsening and anodic oxidation and carries out the aluminum substrate that sealing of hole is processed, and its center line average boldness is at 0. 4-0., 6 μ m;
Infrared ray responsive to exempt from chemical treatment photosensitive composition coating layer dry weight be 8-15mg/dm
2
The protective seam dry weight is 5-20mg/dm
2
The present invention is owing to having used above-mentioned constituent and planographic printing plate manufacture method, the sensitive lithographic plate that obtains has that light sensitivity is high, redeeming a vow to a god property of site is good, the printing down contrast is high after the imaging, be convenient to the front inspection version of machine, and can directly be printed on the machine without any need for the washing processing step, and can obtain the high plurality of advantages such as pressrun
In the multiple copolymer of structure A of the present invention, styrol structural unit has good thermoplasticity, and glass transition temperature is moderate, has the characteristic that is subjected to hot melt molten as bonding agent, can make the picture and text and the basic strong bonded of version of seeing the heat part, thereby strengthen the ink-receptive performance of picture and text part.The content of styrene in multiple copolymer directly affects glass transition temperature and the thermoplasticity of polymkeric substance.Multiple copolymer of the present invention, styrene copolymerized unit A(A and said structure A contradiction herein) weight percent content is 40-70% in grafting multiple copolymer not, preferred 50-60%.
In the multiple copolymer of structure A of the present invention, (methyl) acrylonitrile compolymer unit, it can be selected from Methyl 2-cyanoacrylate, cyanacrylate, vinyl cyanide or methacrylonitrile etc., preferred vinyl cyanide or methacrylonitrile or their potpourri.Synthetic multiple copolymer of the present invention, (methyl) acrylonitrile compolymer unit B weight percent content in grafting multiple copolymer not is preferably 15-25% for being 10%-30%.
In the multiple copolymer of structure A of the present invention, copolymerization units with side chain of ammonia esterification unsaturated double-bond, its unsaturated group fat is crosslinked with the polyfunctionality performed polymer under the effect of light or heat, forms three-dimensional crosslinking structure, can realize that coating changes into hydrophobicly by hydrophilic, realizes plate imaging printing.The bonding agent that contains strong polarity ammonia ester bond has very strong suction-operated to aluminum substrate, can improve the pressrun of plate.In addition, the bonding agent and the base polyurethane prepolymer for use as intermiscibility that contain polyurethane structural are better, and plate is not prone to the appearance that causes pepper point because of the film-forming components dissolubility difference.
Multiple copolymer of the present invention, the copolymerization units weight percent content with side chain of ammonia esterification unsaturated double-bond is 10-30%, preferred 15-25%.
In the multiple copolymer of structure A of the present invention, contain in the vinyl copolymerization units of side chain hydrophilic radical, hydrophilic radical is preferably from amide group, phosphate, pyrrolidone-base, ether etc., preferred hydrophilic radical is amide group, pyrrolidone-base, ether (comprising polyethoxy) or their combination, such as acryloyl morpholine, methoxy polyethylene glycol acrylate, NVP etc.If select side chain to contain the water-soluble monomer of polyethoxy, the polyethoxy molecular weight can not be too large, otherwise the main chain copolyreaction is affected, and molecular weight is too little then water-soluble too poor.Effective molecular weight is 400-10000, preferred 1000-5000, particularly preferably 1500-3000.
Synthetic multiple copolymer of the present invention, the weight percent content of vinyl copolymerization units in multipolymer that contains the side chain hydrophilic radical is 10-30%, preferred 15-25%.
In the multiple copolymer of structure A of the present invention, contain the vinyl copolymerization units of changeable colour group, this changeable colour group is produced when hot by the infrared light radiation at plate, can be from the colourless darkviolet that becomes.And since this multiple copolymer shared large percentage in the photographic layer component easily produce high image density, thereby be conducive to the raising of printing down contrast.
Synthetic multiple copolymer of the present invention, the weight percent content of vinyl copolymerization units in multipolymer that contains the changeable colour group is 10-30%, preferred 15-25%.
The weight-average molecular weight 5000-200000 of the multiple copolymer of structure A of the present invention is preferably 15000-10000, most preferably is 40000-80000.Glass transition temperature is 30-260 ℃, is preferably 40-150 ℃, most preferably is 60-130 ℃.
The object lesson of the multiple copolymer of structure A following (being not limited only to this):
A1:
A2：
A3:
A4:
A5:
A6:
A7:
A8:
A9:
A10:
The performed polymer of photopolymerization of the present invention can use various types of prepolymers, such as polyesters esters of acrylic acid, Epoxy Acrylates, urethane acrylate class, polyether acrylate class, organosilicon preformed polymer class etc., wherein be preferably polyurethane acroleic acid class performed polymer.This prepolymer accounts for the dry weight of filming in light sensitive layer 10-50% is good, preferred 20%～40%.
The monomer of photopolymerization of the present invention can use 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 β-dimethyl-aminoethylmethacrylates and dimethyl one m one isopropenyl benzyl isocyanate ester etc.Preferably use polyfunctional monomer.Polyfunctional monomer accounts for 1～30% of the dry weight of filming in light sensitive layer be good, preferred 10%～20%.
Cationic photopolymerization initiating agent of the present invention is selected from salt, such as sulfosalt, salt compounded of iodine etc.Suitable salt comprises sulfosalt, the inferior maple salt of oxygen, oxygen sulfonium salt, sulfoxide salt, diazo salt and halogen such as iodine anchor salt etc.The instantiation of the salt that is fit to is such as chlorinated diphenyl base salt compounded of iodine, hexafluorophosphoric acid diphenyl iodnium, hexafluoro-antimonic acid diphenyl iodnium, hexafluoro-antimonic acid [4-[(2-hydroxyl myristyl-oxygen base] phenyl] phenyl salt compounded of iodine, tetrafluoro boric acid triphenylsulfonium salt compounded of iodine, octyl group sulfuric acid triphenylsulfonium salt compounded of iodine, hexafluorophosphoric acid-2-methoxyl-4-aminophenyl diazo salt, hexafluoro-antimonic acid Phenoxyphenyl diazo salt etc.The cationic photopolymerization initiating agent accounts for 1～20% of the dry weight of filming in light sensitive layer be good, preferred 5%～15%.
Infrared light radiation absorption dyestuff of the present invention is selected from azo dyes, three arylamine dyestuffs, indoline dye, oxonol dye, cyanine dye, merocyanine dye, indole cyanine dyes, phthalocyanine dye, polythiophene dye, pyrazoline azo dyes, oxazine dye, naphthoquinone dyestuff, anthraquinone dye, quinoneimine dye, methine dyes, porphyrin dye etc.The preferred dyestuff of maximum absorption wavelength about 780 ~ 850nm is conducive to use the infrared laser platemaking machine of main flow in the market to carry out scan exposure like this.Infrared light radiation absorption dyestuff accounts for 1～20% of the dry weight of filming in light sensitive layer be good, preferred 5%～15%.
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.Applicable compound 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 of exposure contacts.Suitable compound or system include but is not limited to; such as a colourless dyestuff, such as the thiazine of acyl group protection, diazine is with oxazine; hydrol (such as the hydrol of Michler), indoles alkene and triarylmethane lactone (such as Crystal Violet lactone).The content of dyestuff in lithographic plate of the present invention should be enough to obtain required version exposed portion and the contrast of unexposed portion.Dye dosage be film dry weight 0.5-5% (weight).
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 affect its performance.
Infrared ray responsive of the present invention exempt from a version base that sensitive lithographic plate that the chemical treatment photosensitive composition makes uses be through electrolyzing and coarsening and anodic oxidation and carry out sealing of hole process after aluminum substrate, 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, make electrolytic solution with the aqueous solution of hydrochloric acid, nitric acid or their salt better.At first aluminium plate is placed in the aqueous solution of 1%～30% NaOH, potassium hydroxide, sodium carbonate, sodium silicate etc., 20～80
OCarry out 5～250 seconds chemical corrosion under the temperature of C.Then in 10～30% nitric acid or sulfuric acid with 20～70
OThe temperature neutralization of C is to remove grey matter.Pass through like this aluminium plate of cleaning, 10～60
OUnder the temperature of C, 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 20～60
OC, oxidization time are 5～250 seconds, to form 1～10 g/m
2Oxide film.The oxide film that forms like this has higher oxide film micropore usually, and adsorptive power is stronger, is easy to adhere to foul.So usually also needing to carry out sealing of hole processes.Sealing of hole is processed and can be used various methods, take 50%～80% volume that reaches sealing oxide film micropore as good.
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 suitable solvent or/and in the water, be made into coating fluid.Suitable solvent has: ethylene glycol ethyl ether, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, 1-Methoxy-2-propyl acetate, diethylene glycol methyl ether, methyl lactate, ethyl lactate, MEK, methyl alcohol, ethanol, isopropyl alcohol, 1-methoxy-2-propanol etc., can be used alone solvent during use, also can use one or more solvent combination.
Exempting from after the chemical treatment photosensitive composition of coating infrared ray responsive of the present invention, also on this layer, be coated with layer protective layer.Protective seam can prevent from hindering the image that is caused by exposure in the photographic layer and form the low molecular compounds such as oxygen that react, in the atmosphere and alkaline matter and be blended in the photographic layer, and photographic layer can be exposed in atmosphere.Therefore; that the penetrability of the low molecular compounds such as oxygen is low for the desired characteristic of this protective seam; and require not hinder in fact the light that uses in the exposure see through and good with the adaptation of photographic layer, can remove at an easy rate in the developing procedure after exposure simultaneously.In addition, also can give to protective seam other performance.For example, light peneration by adding the 780-850nm that uses in the exposure is good and can effectively absorb the colorant (water-soluble dye etc.) of the light outside the 780-850nm scope, can improve the plate-making security of sensitive lithographic plate under white light under the condition that light sensitivity descends not causing.
For can be for the protection of for the material of layer; for example; the preferred good water-soluble high-molecular compound of crystallinity that uses; specifically; known have polyvinyl alcohol (PVA), tygon to adjoin the water-soluble polymerss such as pyrrolidone, acid cellulose class, gelatin, gum arabic, polyacrylic acid; in these materials, when polyvinyl alcohol (PVA) is used as principal ingredient, can bring best result to fundamental characteristics such as the oxygen property cut off, development removability.Can possess the not substituted ethylene alcohol unit that required oxygen cuts off property and water miscible amount as long as contain in the polyvinyl alcohol (PVA) that uses in the protective seam, a part wherein can be replaced by cruel, ether and acetal.In addition, wherein a part equally also can have other copolymerization composition.For the object lesson of polyvinyl alcohol (PVA), can be exemplified as 71-100% hydrolysis and molecular weight and be 300 1 2400 compound.Object lesson has: PVA-105, PVA-110, PVA-117, PVA one 117H. PVA 1, PVA one 124. PVA one 124H. PVA one CS. PVA one CST, PVA one HC. PVA 1, PVA 1, PVA 1, and PVA 1, and PVA 1, PVA 1, and PVA 1, PVA one 217EE, PVA one 217E, PVA one 220E. PVA one 224E, PVA 1, PVA 1, PVA 1 etc.
The composition of protective seam (selection of PVA, the use of adjuvant), coating weight etc. are cut off property, the development removability except considering oxygen, also consider photographic fog and adaptation. scratch resistance and selecting.Generally, the percent hydrolysis of the PVA of use higher (substituted ethylene alcohol unit content is not higher in the protective seam), thickness are thicker, and oxygen cuts off property and becomes higher, and this is conducive to the light sensitivity aspect.In addition, extremely important in the operation of galley with adaptation and the scratch resistance of image section.That is, if hydrophilic being pressed in layer by layer on the oil loving polymer layer that will be comprised of water-soluble polymers then easily occurs to be peeled off by the not enough caused film of clinging power, cause that because of the inhibition of oxygen film solidifies the defectives such as bad in stripping portion branch.The coating weight of protective seam is generally 5-20mg/dm in dry mass
2, be preferably 10-15 mg/dm
2
Below by example explanation the present invention, but be not limited to these examples.
The multipolymer of synthesis example one structure A1 is synthetic
1, monomer is synthetic
In the 500ml there-necked flask, add 19.5g3, the amino benzofuranone of two (4 '-N silomate base phenyl)-6-of 3-, pyridine 5ml, dry tetrahydrofuran 250ml, the heating stirring and dissolving, slowly drip hendecene acyl chlorides 12.0g under the reflux state, behind the back flow reaction 4h, the reaction mixture clear solution that takes on a red color, tetrahydrofuran is reclaimed in atmospheric distillation, concentrate is transferred pH=9 with saturated sodium carbonate solution, and the benzene extraction is washed to neutrality, add activated carbon decolorizing, filter, decompression steams solvent, obtains 3, two (4 '-N, N dimethylamine base the phenyl)-6-hendecene amide group benzofuranone 22g of 3-.
, copolymer A 1 is synthetic
In the four-hole boiling flask of 1000 ml with temperature control heating, mechanical raking, condensing reflux and nitrogen protection device, add DMF and 80.0g styrene that 500 g cross through anhydrous sodium sulfate drying; the 40g vinyl cyanide; 40.0g3; two (the 4 '-N of 3-; N dimethylamine base phenyl)-6-hendecene amide group benzofuranone; the 20g hydroxyethyl methylacrylate, the 20g methoxy polyethylene glycol methacrylate-styrene polymer.Nitrogen protects and adds 1.0gAIBN (azoisobutyronitrile) after heating is stirred to dissolution of solid, 70 ℃ of reactions were added 0.5gAIBN after 3 hours, reacted to add dibutyl tin laurate 0.1g, 21.5gMOI after 4 hours again, nitroxyl free radical piperidine alcohols 0.1g, afterreaction finished in 1 hour.Obtain copolymer A 1, solid content is 30.7% weight
The multipolymer of synthesis example two structure A2 is synthetic
1, monomer is synthetic
In the 500ml there-necked flask, add 19.5g3, the amino benzofuranone of two (4 '-N silomate base phenyl)-6-of 3-, pyridine 5ml, dry tetrahydrofuran 250ml, the heating stirring and dissolving, slowly drip hendecene acyl chlorides 12.5g under the reflux state, behind the back flow reaction 4h, the reaction mixture clear solution that takes on a red color, tetrahydrofuran is reclaimed in atmospheric distillation, concentrate is transferred pH=9 with saturated sodium carbonate solution, and the benzene extraction is washed to neutrality, add activated carbon decolorizing, filter, decompression steams solvent, obtains 3, two (4 '-N, N dimethylamine base the phenyl)-6-hendecene amide group benzofuranone 23g of 3-.
, copolymer A 2 is synthetic
In the four-hole boiling flask of 1000 ml with temperature control heating, mechanical raking, condensing reflux and nitrogen protection device, add DMF and 100.0g styrene that 500 g cross through anhydrous sodium sulfate drying; the 20g methacrylonitrile; 40.0g3; two (the 4 '-N of 3-; N dimethylamine base phenyl)-6-hendecene amide group benzofuranone; the 20g hydroxyethyl methylacrylate, the 20g methoxy polyethylene glycol methacrylate-styrene polymer.Nitrogen protects and adds 1.0gAIBN (azoisobutyronitrile) after heating is stirred to dissolution of solid, 70 ℃ of reactions were added 0.5gAIBN after 3 hours, reacted to add dibutyl tin laurate 0.1g, 21.5gMOI after 4 hours again, nitroxyl free radical piperidine alcohols 0.1g, afterreaction finished in 1 hour.Obtain copolymer A 2, solid content is 30.7% weight
The multipolymer of synthesis example three structure A3 is synthetic
1, monomer is synthetic
In the 500ml there-necked flask, add 19.5g3, the amino benzofuranone of two (4 '-N silomate base phenyl)-6-of 3-, pyridine 5ml, dry tetrahydrofuran 250ml, the heating stirring and dissolving, slowly drip nonene acyl chlorides 12.0g under the reflux state, behind the back flow reaction 4h, the reaction mixture clear solution that takes on a red color, tetrahydrofuran is reclaimed in atmospheric distillation, concentrate is transferred pH=9 with saturated sodium carbonate solution, and the benzene extraction is washed to neutrality, add activated carbon decolorizing, filter, decompression steams solvent, obtains 3, two (4 '-N, N dimethylamine base the phenyl)-6-nonenamide base benzofuranone 22g of 3-.
, copolymer A 3 is synthetic
In the four-hole boiling flask of 1000 ml with temperature control heating, mechanical raking, condensing reflux and nitrogen protection device, add DMF and 120.0g styrene that 500 g cross through anhydrous sodium sulfate drying; the 20g methacrylonitrile; 20.0g3; two (the 4 '-N of 3-; N dimethylamine base phenyl)-6-nonenamide base benzofuranone; the 20g hydroxyethyl methylacrylate, the 20g methoxy polyethylene glycol methacrylate-styrene polymer.Nitrogen protects and adds 1.0gAIBN (azoisobutyronitrile) after heating is stirred to dissolution of solid, 70 ℃ of reactions were added 0.5gAIBN after 3 hours, reacted to add dibutyl tin laurate 0.1g, 21.5gMOI after 4 hours again, nitroxyl free radical piperidine alcohols 0.1g, afterreaction finished in 1 hour.Obtain copolymer A 3, solid content is 30.7% weight
The multipolymer of synthesis example four structure A4 is synthetic
1, monomer is synthetic
In the 500ml there-necked flask, add 19.5g3, the amino benzofuranone of two (4 '-N silomate base phenyl)-6-of 3-, pyridine 5ml, dry tetrahydrofuran 250ml, the heating stirring and dissolving, slowly drip nonene acyl chlorides 12.0g under the reflux state, behind the back flow reaction 4h, the reaction mixture clear solution that takes on a red color, tetrahydrofuran is reclaimed in atmospheric distillation, concentrate is transferred pH=9 with saturated sodium carbonate solution, and the benzene extraction is washed to neutrality, add activated carbon decolorizing, filter, decompression steams solvent, obtains 3, two (4 '-N, N dimethylamine base the phenyl)-6-nonenamide base benzofuranone 22g of 3-.
, copolymer A 4 is synthetic
In the four-hole boiling flask of 1000 ml with temperature control heating, mechanical raking, condensing reflux and nitrogen protection device, add DMF and 80.0g styrene that 500 g cross through anhydrous sodium sulfate drying; the 60g methacrylonitrile; 20.0g3; two (the 4 '-N of 3-; N dimethylamine base phenyl)-6-nonenamide base benzofuranone; the 20g hydroxyethyl methylacrylate, the 20g methoxy polyethylene glycol methacrylate-styrene polymer.Nitrogen protects and adds 1.0gAIBN (azoisobutyronitrile) after heating is stirred to dissolution of solid, 70 ℃ of reactions were added 0.5gAIBN after 3 hours, reacted to add dibutyl tin laurate 0.1g, 21.5gMOI after 4 hours again, nitroxyl free radical piperidine alcohols 0.1g, afterreaction finished in 1 hour.Obtain copolymer A 4, solid content is 30.7% weight
The multipolymer of synthesis example five structure A5 is synthetic
1, monomer is synthetic
In the 500ml there-necked flask, add 19.5g3, the amino benzofuranone of two (4 '-N silomate base phenyl)-6-of 3-, pyridine 5ml, dry tetrahydrofuran 250ml, the heating stirring and dissolving, slowly drip hexene acyl chlorides 12.5g under the reflux state, behind the back flow reaction 4h, the reaction mixture clear solution that takes on a red color, tetrahydrofuran is reclaimed in atmospheric distillation, concentrate is transferred pH=9 with saturated sodium carbonate solution, and the benzene extraction is washed to neutrality, add activated carbon decolorizing, filter, decompression steams solvent, obtains 3, two (4 '-N, N dimethylamine base the phenyl)-6-hexenoyl amido benzofuranone 23g of 3-.
, copolymer A 5 is synthetic
In the four-hole boiling flask of 1000 ml with temperature control heating, mechanical raking, condensing reflux and nitrogen protection device, add DMF and 80.0g styrene that 500 g cross through anhydrous sodium sulfate drying; the 20g methacrylonitrile; 60.0g3; two (the 4 '-N of 3-; N dimethylamine base phenyl)-6-hexenoyl amido benzofuranone; the 20g hydroxyethyl methylacrylate, the 20g methoxy polyethylene glycol methacrylate-styrene polymer.Nitrogen protects and adds 1.0gAIBN (azoisobutyronitrile) after heating is stirred to dissolution of solid, 70 ℃ of reactions were added 0.5gAIBN after 3 hours, reacted to add dibutyl tin laurate 0.1g, 21.5gMOI after 4 hours again, nitroxyl free radical piperidine alcohols 0.1g, afterreaction finished in 1 hour.Obtain copolymer A 5, solid content is 30.7% weight
The multipolymer of synthesis example six structure A6 is synthetic
1, monomer is synthetic
In the 500ml there-necked flask, add 19.5g3, the amino benzofuranone of two (4 '-N silomate base phenyl)-6-of 3-, pyridine 5ml, dry tetrahydrofuran 250ml, the heating stirring and dissolving, slowly drip hexene acyl chlorides 12.5g under the reflux state, behind the back flow reaction 4h, the reaction mixture clear solution that takes on a red color, tetrahydrofuran is reclaimed in atmospheric distillation, concentrate is transferred pH=9 with saturated sodium carbonate solution, and the benzene extraction is washed to neutrality, add activated carbon decolorizing, filter, decompression steams solvent, obtains 3, two (4 '-N, N dimethylamine base the phenyl)-6-hexenoyl amido benzofuranone 23g of 3-.
, copolymer A 6 is synthetic
In the four-hole boiling flask of 1000 ml with temperature control heating, mechanical raking, condensing reflux and nitrogen protection device, add DMF and 80.0g styrene that 500 g cross through anhydrous sodium sulfate drying; the 40g methacrylonitrile; 20.0g3; two (the 4 '-N of 3-; N dimethylamine base phenyl)-6-hexenoyl amido benzofuranone; the 40g hydroxyethyl methylacrylate, the 20g methoxy polyethylene glycol methacrylate-styrene polymer.Nitrogen protects and adds 1.0gAIBN (azoisobutyronitrile) after heating is stirred to dissolution of solid, 70 ℃ of reactions were added 0.5gAIBN after 3 hours, reacted to add dibutyl tin laurate 0.1g, 21.5gMOI after 4 hours again, nitroxyl free radical piperidine alcohols 0.1g, afterreaction finished in 1 hour.Obtain copolymer A 6, solid content is 30.7% weight
The multipolymer of synthesis example seven structure A7 is synthetic
1, monomer is synthetic
In the 500ml there-necked flask, add 19.5g3, the amino benzofuranone of two (4 '-N silomate base phenyl)-6-of 3-, pyridine 5ml, dry tetrahydrofuran 250ml, the heating stirring and dissolving, slowly drip hendecene acyl chlorides 12.5g under the reflux state, behind the back flow reaction 4h, the reaction mixture clear solution that takes on a red color, tetrahydrofuran is reclaimed in atmospheric distillation, concentrate is transferred pH=9 with saturated sodium carbonate solution, and the benzene extraction is washed to neutrality, add activated carbon decolorizing, filter, decompression steams solvent, obtains 3, two (4 '-N, N dimethylamine base the phenyl)-6-hendecene amide group benzofuranone 23g of 3-.
, copolymer A 7 is synthetic
In the four-hole boiling flask of 1000 ml with temperature control heating, mechanical raking, condensing reflux and nitrogen protection device, add DMF and 80.0g styrene that 500 g cross through anhydrous sodium sulfate drying; the 40g vinyl cyanide; 20.0g3; two (the 4 '-N of 3-; N dimethylamine base phenyl)-6-hendecene amide group benzofuranone; the 20g hydroxyethyl methylacrylate, the 40g methoxy polyethylene glycol methacrylate-styrene polymer.Nitrogen protects and adds 1.0gAIBN (azoisobutyronitrile) after heating is stirred to dissolution of solid, 70 ℃ of reactions were added 0.5gAIBN after 3 hours, reacted to add dibutyl tin laurate 0.1g, 21.5gMOI after 4 hours again, nitroxyl free radical piperidine alcohols 0.1g, afterreaction finished in 1 hour.Obtain copolymer A 7, solid content is 30.7% weight
The multipolymer of synthesis example eight structure A8 is synthetic
1, monomer is synthetic
In the 500ml there-necked flask, add 19.5g3, the amino benzofuranone of two (4 '-N silomate base phenyl)-6-of 3-, pyridine 5ml, dry tetrahydrofuran 250ml, the heating stirring and dissolving, slowly drip hendecene acyl chlorides 12.5g under the reflux state, behind the back flow reaction 4h, the reaction mixture clear solution that takes on a red color, tetrahydrofuran is reclaimed in atmospheric distillation, concentrate is transferred pH=9 with saturated sodium carbonate solution, and the benzene extraction is washed to neutrality, add activated carbon decolorizing, filter, decompression steams solvent, obtains 3, two (4 '-N, N dimethylamine base the phenyl)-6-hendecene amide group benzofuranone 23g of 3-.
, copolymer A 8 is synthetic
In the four-hole boiling flask of 1000 ml with temperature control heating, mechanical raking, condensing reflux and nitrogen protection device, add DMF and 80.0g styrene that 500 g cross through anhydrous sodium sulfate drying; the 20g vinyl cyanide; 20.0g3; two (the 4 '-N of 3-; N dimethylamine base phenyl)-6-hendecene amide group benzofuranone; the 60g hydroxyethyl methylacrylate, the 20g methoxy polyethylene glycol methacrylate-styrene polymer.Nitrogen protects and adds 1.0gAIBN (azoisobutyronitrile) after heating is stirred to dissolution of solid, 70 ℃ of reactions were added 0.5gAIBN after 3 hours, reacted to add dibutyl tin laurate 0.1g, 21.5gMOI after 4 hours again, nitroxyl free radical piperidine alcohols 0.1g, afterreaction finished in 1 hour.Obtain copolymer A 8, solid content is 30.7% weight
The multipolymer of synthesis example nine structure A9 is synthetic
1, monomer is synthetic
In the 500ml there-necked flask, add 19.5g3, the amino benzofuranone of two (4 '-N silomate base phenyl)-6-of 3-, pyridine 5ml, dry tetrahydrofuran 250ml, the heating stirring and dissolving, slowly drip hendecene acyl chlorides 12.5g under the reflux state, behind the back flow reaction 4h, the reaction mixture clear solution that takes on a red color, tetrahydrofuran is reclaimed in atmospheric distillation, concentrate is transferred pH=9 with saturated sodium carbonate solution, and the benzene extraction is washed to neutrality, add activated carbon decolorizing, filter, decompression steams solvent, obtains 3, two (4 '-N, N dimethylamine base the phenyl)-6-hendecene amide group benzofuranone 23g of 3-.
, copolymer A 9 is synthetic
In the four-hole boiling flask of 1000 ml with temperature control heating, mechanical raking, condensing reflux and nitrogen protection device, add DMF and 80.0g styrene that 500 g cross through anhydrous sodium sulfate drying; the 20g methacrylonitrile; 20.0g3; two (the 4 '-N of 3-; N dimethylamine base phenyl)-6-hendecene amide group benzofuranone; the 20g hydroxy-ethyl acrylate, the 60g methoxy polyethylene glycol methacrylate-styrene polymer.Nitrogen protects and adds 1.0gAIBN (azoisobutyronitrile) after heating is stirred to dissolution of solid, 70 ℃ of reactions were added 0.5gAIBN after 3 hours, reacted to add dibutyl tin laurate 0.1g, 21.5gMOI after 4 hours again, nitroxyl free radical piperidine alcohols 0.1g, afterreaction finished in 1 hour.Obtain copolymer A 9, solid content is 30.7% weight
The multipolymer of synthesis example ten structure A10 is synthetic
1, monomer is synthetic
In the 500ml there-necked flask, add 19.5g3, the amino benzofuranone of two (4 '-N silomate base phenyl)-6-of 3-, pyridine 5ml, dry tetrahydrofuran 250ml, the heating stirring and dissolving, slowly drip hendecene acyl chlorides 12.5g under the reflux state, behind the back flow reaction 4h, the reaction mixture clear solution that takes on a red color, tetrahydrofuran is reclaimed in atmospheric distillation, concentrate is transferred pH=9 with saturated sodium carbonate solution, and the benzene extraction is washed to neutrality, add activated carbon decolorizing, filter, decompression steams solvent, obtains 3, two (4 '-N, N dimethylamine base the phenyl)-6-hendecene amide group benzofuranone 23g of 3-.
, copolymer A 10 is synthetic
In the four-hole boiling flask of 1000 ml with temperature control heating, mechanical raking, condensing reflux and nitrogen protection device, add DMF and 100.0g styrene that 500 g cross through anhydrous sodium sulfate drying; the 40g methacrylonitrile; 20.0g3; two (the 4 '-N of 3-; N dimethylamine base phenyl)-6-hendecene amide group benzofuranone; the 20g hydroxyethyl methylacrylate, the 20g methoxy polyethylene glycol methacrylate-styrene polymer.Nitrogen protects and adds 1.0gAIBN (azoisobutyronitrile) after heating is stirred to dissolution of solid, 70 ℃ of reactions were added 0.5gAIBN after 3 hours, reacted to add dibutyl tin laurate 0.1g, 21.5gMOI after 4 hours again, nitroxyl free radical piperidine alcohols 0.1g, afterreaction finished in 1 hour.Obtain copolymer A 10, solid content is 30.7% weight
Embodiment 1
The preparation of version base: the A1050 calendering aluminium plate of purity 99.5%, thick 0.3mm, in 5% sodium hydrate aqueous solution 70
OEtch is 20 seconds under the C, with after the flowing water flushing, neutralizes with 1% aqueous solution of nitric acid immediately.Then in 1% aqueous hydrochloric acid solution, 40
OUse sine wave alternating current with 50A/dm under the C
2Current density electrolyzing and coarsening 16 seconds.Follow 40
OUnder the C, with in 5% the sodium hydrate aqueous solution and 10 seconds.Washing.At last 30
OUnder the C, the aqueous sulfuric acid with 20% is with 15A/dm
2Current density, anodic oxidation 20 seconds.Washing.80
OCarrying out sealing of hole with 5% sodium silicate aqueous solution under the C processed 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
The photographic layer coating: the sensitization liquid on the version base of above-mentioned process hydrophilicity-imparting treatment below the extrusion coated, then 100
ODrying is 60 seconds under the C.Obtain 10mg/dm
2The coating dry weight.Component (each component is by weight) below sensitization liquid uses:
Structure is the polymkeric substance 8.000 of A1
Polyurethane acroleic acid prepolymer 1.440
Pentaerythritol triacrylate 0.480
Hexafluorophosphoric acid sulfonium salt 0.240.
Infrared absorbing dye D1 0.240
BYK-333 ０.０08
1-methoxy-2-propanol 69.592
The protective seam coating: the protective seam solution that extrusion coated is following on photographic layer obtained above, then 110
ODrying is 60 seconds under the C.Obtain 10mg/dm
2Coating dry weight (each component by weight).
PVA205 2.0
BYK333 0.04
H
2O 47.96
Be weight percentage 30.0% DMF solution (A2 in following instance and the comparative example, A3, A4, A5, A6, A7, A8, A9, A10 are identical therewith) of the polymkeric substance of structural formula A1
The structure of infrared absorbing dye D1 is as follows:
The plate that obtains like this on the all-victorious thermosensitive CTP platemaking machine of Kodak with 120mJ/cm
2Energy expose.Then, measure expose on the space of a whole page on the spot part and the unexposed density of part on the spot with Ai Seli 528, its difference is the printing down contrast, is designated as Δ OD, then directly locks up printing.Its performance is listed in the table one of back.
Embodiment 2
With top identical method preparation version base, photographic layer and protective seam.The following component of sensitization liquid:
Structure is the polymkeric substance 4.800 of A2
Polyurethane acroleic acid prepolymer 0.960
Pentaerythritol triacrylate 0.480
Hexafluorophosphoric acid sulfonium salt 0.960
Infrared absorbing dye D1 0.960
BYK-333 ０.008
1-methoxy-2-propanol 71.832
The plate that obtains like this on the all-victorious thermosensitive CTP platemaking machine of Kodak with 100mJ/cm
2Energy expose.Then, measure expose on the space of a whole page on the spot part and the unexposed density of part on the spot with Ai Seli 528, its difference is the printing down contrast, is Δ OD, then directly locks up printing.Its performance is listed in the table one of back.
Embodiment 3
With top identical method preparation version base, photographic layer and protective seam.The following component of sensitization liquid:
Structure is the polymkeric substance 11.200 of A3
Polyurethane acroleic acid prepolymer 0.480
Pentaerythritol triacrylate 0.480
Hexafluorophosphoric acid sulfonium salt 0.240
Infrared absorbing dye D1 0.240
BYK-333 ０.008
1-methoxy-2-propanol 67.352
The plate that obtains like this on the all-victorious thermosensitive CTP platemaking machine of Kodak with 140mJ/cm
2Energy expose.Then, measure expose on the space of a whole page on the spot part and the unexposed density of part on the spot with Ai Seli 528, its difference is the printing down contrast, is Δ OD, then directly locks up printing.Its performance is listed in the table one of back.
Embodiment 4
With top identical method preparation version base, photographic layer and protective seam.The following component of sensitization liquid:
Structure is the polymkeric substance 4.800 of A4
Polyurethane acroleic acid prepolymer 2.400
Pentaerythritol triacrylate 0.480
Hexafluorophosphoric acid sulfonium salt 0.240
Infrared absorbing dye D1 0.240
BYK-333 ０.008
1-methoxy-2-propanol 71.832
The plate that obtains like this on the all-victorious thermosensitive CTP platemaking machine of Kodak with 100mJ/cm
2Energy expose.Then, measure expose on the space of a whole page on the spot part and the unexposed density of part on the spot with Ai Seli 528, its difference is the printing down contrast, is Δ OD, then directly locks up printing.Its performance is listed in the table one of back.
Embodiment 5
With top identical method preparation version base, photographic layer and protective seam.The following component of sensitization liquid:
Structure is the polymkeric substance 8.640 of A5
Polyurethane acroleic acid prepolymer 0.960
Pentaerythritol triacrylate 0.720
Hexafluorophosphoric acid sulfonium salt 0.048
Infrared absorbing dye D1 0.480
BYK-333 ０.008
1-methoxy-2-propanol 69.144
The plate that obtains like this on the all-victorious thermosensitive CTP platemaking machine of Kodak with 140mJ/cm
2Energy expose.Then, measure expose on the space of a whole page on the spot part and the unexposed density of part on the spot with Ai Seli 528, its difference is the printing down contrast, is Δ OD, then directly locks up printing.Its performance is listed in the table one of back.
Embodiment 6
With top identical method preparation version base, photographic layer and protective seam.The following component of sensitization liquid:
Structure is the polymkeric substance 6.400 of A6
Polyurethane acroleic acid prepolymer 1.392
Pentaerythritol triacrylate 0.960
Hexafluorophosphoric acid sulfonium salt 0.480
Infrared absorbing dye D1 0.048
BYK-333 ０.008
1-methoxy-2-propanol 70.712
The plate that obtains like this on the all-victorious thermosensitive CTP platemaking machine of Kodak with 120mJ/cm
2Energy expose.Then, measure expose on the space of a whole page on the spot part and the unexposed density of part on the spot with Ai Seli 528, its difference is the printing down contrast, is Δ OD, then directly locks up printing.Its performance is listed in the table one of back.
Embodiment 7
With top identical method preparation version base, photographic layer and protective seam.The following component of sensitization liquid:
Structure is the polymkeric substance 4.800 of A7
Polyurethane acroleic acid prepolymer 0.960
Pentaerythritol triacrylate 1.440
Hexafluorophosphoric acid sulfonium salt 0.480
Infrared absorbing dye D1 0.480
BYK-333 ０.008
1-methoxy-2-propanol 71.832
The plate that obtains like this on the all-victorious thermosensitive CTP platemaking machine of Kodak with 130mJ/cm
2Energy expose.Then, measure expose on the space of a whole page on the spot part and the unexposed density of part on the spot with Ai Seli 528, its difference is the printing down contrast, is Δ OD, then directly locks up printing.Its performance is listed in the table one of back.
Embodiment 8
With top identical method preparation version base, photographic layer and protective seam.The following component of sensitization liquid:
Structure is the polymkeric substance 8.000 of A8
Polyurethane acroleic acid prepolymer 1.440
Pentaerythritol triacrylate 0.480
Hexafluorophosphoric acid sulfonium salt 0.240
Infrared absorbing dye D1 0.240
BYK-333 ０.008
1-methoxy-2-propanol 69.592
The plate that obtains like this on the all-victorious thermosensitive CTP platemaking machine of Kodak with 140mJ/cm
2Energy expose.Then, measure expose on the space of a whole page on the spot part and the unexposed density of part on the spot with Ai Seli 528, its difference is the printing down contrast, is Δ OD, then directly locks up printing.Its performance is listed in the table one of back.
Embodiment 9
With top identical method preparation version base, photographic layer and protective seam.The following component of sensitization liquid:
Structure is the polymkeric substance 8.000 of A9
Polyurethane acroleic acid prepolymer 1.440
Pentaerythritol triacrylate 0.480
Hexafluorophosphoric acid sulfonium salt 0.240
Infrared absorbing dye D1 0.240
BYK-333 ０.008
1-methoxy-2-propanol 69.592
The plate that obtains like this on the all-victorious thermosensitive CTP platemaking machine of Kodak with 140mJ/cm
2Energy expose.Then, measure expose on the space of a whole page on the spot part and the unexposed density of part on the spot with Ai Seli 528, its difference is the printing down contrast, is Δ OD, then directly locks up printing.Its performance is listed in the table one of back.
Embodiment 10
With top identical method preparation version base, photographic layer and protective seam.The following component of sensitization liquid:
Structure is the polymkeric substance 8.000 of A10
Polyurethane acroleic acid prepolymer 1.440
Pentaerythritol triacrylate 0.480
Hexafluorophosphoric acid sulfonium salt 0.240
Infrared absorbing dye D1 0.240
BYK-333 ０.008
1-methoxy-2-propanol 69.592
The plate that obtains like this on the all-victorious thermosensitive CTP platemaking machine of Kodak with 140mJ/cm
2Energy expose.Then, measure expose on the space of a whole page on the spot part and the unexposed density of part on the spot with Ai Seli 528, its difference is the printing down contrast, is Δ OD, then directly locks up printing.Its performance is listed in the table one of back.
Embodiment 11
Prepare version base, photographic layer and protective seam with embodiment 1 identical method.Just making the center line average boldness of version base is 0.4um
The plate that obtains like this on the all-victorious thermosensitive CTP platemaking machine of Kodak with 120mJ/cm
2Energy expose.Then, measure expose on the space of a whole page on the spot part and the unexposed density of part on the spot with Ai Seli 528, its difference is the printing down contrast, is Δ OD, then directly locks up printing.Its performance is listed in the table one of back.
Embodiment 12
Prepare version base, photographic layer and protective seam with embodiment 1 identical method.Just making the center line average boldness of version base is 0.6um
The plate that obtains like this on the all-victorious thermosensitive CTP platemaking machine of Kodak with 120mJ/cm
2Energy expose.Then, measure expose on the space of a whole page on the spot part and the unexposed density of part on the spot with Ai Seli 528, its difference is the printing down contrast, is Δ OD, then directly locks up printing.Its performance is listed in the table one of back.
Embodiment 13
Prepare version base, photographic layer and protective seam with embodiment 1 identical method.Just make the dry coating of photographic layer heavily be 18mg/dm
2
The plate that obtains like this on the all-victorious thermosensitive CTP platemaking machine of Kodak with 120mJ/cm
2Energy expose.Then, measure expose on the space of a whole page on the spot part and the unexposed density of part on the spot with Ai Seli 528, its difference is the printing down contrast, is Δ OD, then directly locks up printing.Its performance is listed in the table one of back.
Embodiment 14
Prepare version base, photographic layer and protective seam with embodiment 1 identical method.The dry coating weight that just makes photographic layer is 15mg/dm
2
The plate that obtains like this on the all-victorious thermosensitive CTP platemaking machine of Kodak with 120mJ/cm
2Energy expose.Then, measure expose on the space of a whole page on the spot part and the unexposed density of part on the spot with Ai Seli 528, its difference is the printing down contrast, is Δ OD, then directly locks up printing.Its performance is listed in the table one of back.
Embodiment 15
Prepare version base, photographic layer and protective seam with embodiment 1 identical method.The dry coating weight that just makes protective seam is 5mg/dm
2
The plate that obtains like this on the all-victorious thermosensitive CTP platemaking machine of Kodak with 120mJ/cm
2Energy expose.Then, measure expose on the space of a whole page on the spot part and the unexposed density of part on the spot with Ai Seli 528, its difference is the printing down contrast, is Δ OD, then directly locks up printing.Its performance is listed in the table one of back.
Embodiment 16
Prepare version base, photographic layer and protective seam with embodiment 1 identical method.The dry coating weight that just makes protective seam is 20mg/dm
2
The plate that obtains like this on the all-victorious thermosensitive CTP platemaking machine of Kodak with 120mJ/cm
2Energy expose.Then, measure expose on the space of a whole page on the spot part and the unexposed density of part on the spot with Ai Seli 528, its difference is the printing down contrast, is Δ OD, then directly locks up printing.Its performance is listed in the table one of back.
Comparative example 1
Prepare version base, photographic layer and protective seam with embodiment 1 identical method.Component below the sensitization coating fluid uses:
Quadripolymer 8.000 among the A except the copolymerization units of changeable colour group
Polyurethane acroleic acid prepolymer 1.440
Pentaerythritol triacrylate 0.480
Hexafluorophosphoric acid sulfonium salt 0.240.
Infrared absorbing dye D1 0.240
BYK-333 ０.０08
1-methoxy-2-propanol 69.592
The plate that obtains like this on the all-victorious thermosensitive CTP platemaking machine of Kodak with 120mJ/cm
2Energy expose.Then, measure expose on the space of a whole page on the spot part and the unexposed density of part on the spot with Ai Seli 528, its difference is the printing down contrast, is Δ OD, then directly locks up printing.Its performance is listed in the table one of back.
Comparative example 2
With method preparation version base, photographic layer and the hydrophilic layer identical with example 1.Be the following component of sensitization liquid:
Structure is the polymkeric substance 8.000 of A1
Polyurethane acroleic acid prepolymer 1.440
Pentaerythritol triacrylate 0.480
Hexafluorophosphoric acid sulfonium salt 0.240.
Triazine B 0.240
BYK-333 ０.０08
1-methoxy-2-propanol 69.592
The plate that obtains like this on the all-victorious thermosensitive CTP platemaking machine of Kodak with 300mJ/cm
2Energy expose.Then, measure expose on the space of a whole page on the spot part and the unexposed density of part on the spot with Ai Seli 528, its difference is the printing down contrast, is Δ OD, then directly locks up printing.Its performance is listed in the table one of back.
Comparative example 3
Prepare version base, photographic layer and protective seam with embodiment 1 identical method.Just making the center line average boldness of version base is 0.70um,
The plate that obtains like this on the all-victorious thermosensitive CTP platemaking machine of Kodak with 120mJ/cm
2Energy expose.Then, measure expose on the space of a whole page on the spot part and the unexposed density of part on the spot with Ai Seli 528, its difference is the printing down contrast, is Δ OD, then directly locks up printing.Its performance is listed in the table one of back.
Comparative example 4
Prepare version base, photographic layer and protective seam with embodiment 1 identical method.The dry coating weight that just makes protective seam is 25mg/dm
2
The plate that obtains like this on the all-victorious thermosensitive CTP platemaking machine of Kodak with 120mJ/cm
2Energy expose.Then, measure expose on the space of a whole page on the spot part and the unexposed density of part on the spot with Ai Seli 528, its difference is the printing down contrast, is Δ OD, then directly locks up printing.Its performance is listed in the table one of back.
Table one
Claims (10)
1. negative graph photosensitive composition, it is characterized in that: it comprises the water soluble thermo-crosslinked multipolymer that side chain contains the changeable colour group, the performed polymer of photopolymerization, polyfunctional monomer, cationic photopolymerization initiating agent and infrared light radiation absorption dyestuff, by weight percentage, the water soluble thermo-crosslinked resin that side chain contains the changeable colour group accounts for the 30-70% of constituent solid amount, the performed polymer of photopolymerization accounts for the 10-50% of constituent solid amount, polyfunctional monomer accounts for the 10-30% of constituent solid amount, the cationic photopolymerization initiating agent accounts for the 1-20% of constituent solid amount, and infrared light radiation absorption dyestuff accounts for the 1-20% of constituent solid amount.
2. photosensitive composition according to claim 1, it is characterized in that: by weight percentage, the consumption that described side chain contains the water soluble thermo-crosslinked multipolymer of changeable colour group accounts for the 40-60% of constituent solid amount, the performed polymer of photopolymerization accounts for the 20-40% of constituent solid amount, polyfunctional monomer accounts for the 10-20% of constituent solid amount, the cationic photopolymerization initiating agent accounts for the 5-15% of constituent solid amount, and infrared light radiation absorption dyestuff accounts for the 5-15% of constituent solid amount.
3. photosensitive composition according to claim 1 and 2, it is characterized in that: described side chain contains the water soluble thermo-crosslinked multipolymer of changeable colour group, and following structure is arranged:
R1, R2 are H atom or methyl, and R3 is CH
2=C (CH
3) the COOCH2CH2NCO-group, R4 is amide group, ether or pyrrolidone-base, X is the integer of 3-8;
M, n, o, p, q are the percent by weight of corresponding copolymerization units, and the m proportion is that 40 ~ 60%, n proportion is that 10 ~ 30%, o proportion is that 10 ~ 30%, p proportion is that 10 ~ 30%, q proportion is 10 ~ 30%.
4. photosensitive composition according to claim 1 and 2, it is characterized in that: the performed polymer of described photopolymerization is polyurethane acroleic acid class performed polymer.
5. photosensitive composition according to claim 1 and 2, it is characterized in that: described polyfunctional monomer is selected from acrylic monomer, polyurethane acroleic acid class monomer or propylene oxide acid monomers; Described cationic photopolymerization initiating agent is selected from one or more of salt compounded of iodine, sulfosalt, microcosmic salt, selenium salt; The heat decomposition temperature of described cationic photopolymerization initiating agent is 150 ~ 200
oC; Described infrared light radiation absorption dyestuff is a kind of cyanine dyes that is absorbed in 750 ~ 850nm.
6. sensitive lithographic plate made from claim 1 or 2 described negative graph photosensitive compositions; it is characterized in that; it comprises: (1) aluminum substrate support; (2) above-mentioned negative graph photosensitive composition coating layer, and (3) above-mentioned negative graph photosensitive composition coating layer is at protective seam the same side and on it.
7. the sensitive lithographic plate made of negative graph photosensitive composition according to claim 9 is characterized in that: the support of sensitive lithographic plate is through electrolyzing and coarsening and anodic oxidation and carries out the aluminum substrate that sealing of hole is processed, and its center line average boldness is at 0. 4-0., 6 μ m.
8. the sensitive lithographic plate made of negative graph photosensitive composition according to claim 9, it is characterized in that: above-mentioned negative graph photosensitive composition coating layer dry weight is 8-15mg/dm
2
9. the sensitive lithographic plate made of negative graph photosensitive composition according to claim 9, it is characterized in that: described protective seam dry weight is 5-20mg/dm
2
10. the sensitive lithographic plate made of described negative graph photosensitive composition according to claim 9 is characterized in that, this sensitive lithographic plate can directly be lockd up on the printing machine without any washing processing step and print after using thermosensitive CTP platemaking machine scan exposure.
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| CN201210426127.0A CN102902161B (en) | 2012-10-31 | 2012-10-31 | Negative graph photosensitive composition and the sensitive lithographic plate made of it |
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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. |