CN104730862A - Negative image photosensitive composition and temperature-sensitive plate manufactured from same - Google Patents
Negative image photosensitive composition and temperature-sensitive plate manufactured from same Download PDFInfo
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- CN104730862A CN104730862A CN201310706605.8A CN201310706605A CN104730862A CN 104730862 A CN104730862 A CN 104730862A CN 201310706605 A CN201310706605 A CN 201310706605A CN 104730862 A CN104730862 A CN 104730862A
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Abstract
The invention discloses a negative image photosensitive composition. The negative image photosensitive composition comprises a nano particles-containing uretidione prepolymer, a polyfunctional monomer, a thermal polymerization agent, an infrared absorbent and a promoter, wherein in terms of weight percentage, discrete micron particles account for 30-70% relative to the total amount of the solid composition, the uretidione 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 thermal polymerization agent accounts for 1-20% relative to the total amount of the solid composition, the infrared absorbent accounts for 10-30% relative to the total amount of the solid composition, and the organic metal promoter accounts for 10-30% relative to the total amount of the solid composition. The photosensitive composition solves the disadvantages of poor solvent-resistance capability and pressrun capability of the printing plate materials existed in a processing-free temperature-sensitive CTP (Computer to Plate) plate, difficultly dissolved high-molecular resin with a net structure is added in the temperature-sensitive composition, so that good wear resistance can be obtained, and pressrun capability of the printing plate materials can be increased.
Description
Technical field
The present invention relates to a kind of negative graph photosensitive composition, and a kind of flushing-free is directly printed on the machine thermosensitive CTP sensitive lithographic plate.
Background technology
Lithography technique moves towards Computer To Plate 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.
CTP plate-making technology needs one " developing process ", there is 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 construction, 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 curing, 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 polymkeric substance of temperature-sensitive (as poly-oxinane methacrylate, with aryldiazosulphonate base ethylene copolymer).The convertible polymkeric substance of temperature-sensitive is adopted to form thermo-sensitive material.Before imaging, the water-soluble solution of heat-sensitive layer.During imaging, infrared absorbing agents absorbing laser energy, the heat of generation causes diazo to decompose, and makes to be exposed temperature-sensitive multipolymer and becomes hydrophobic from hydrophilic, thus form oleophylic district.And unexposed area temperature-sensitive multipolymer 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: the technology being real Commercialization application in current third generation processless CTP.The agent of thermographic middle infrared absorption 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 water wettability.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.
Chemical treatment CTP version is exempted from exploitation, and one of gordian technique is plate precursor and the organic exploitation of function.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 EP2006-5-2406114475.4 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, need add anti-micro-raw agent; Kodak US2005-8-311/196,124, introduce a kind of comprise polyalkylene oxide hydrocarbon segment and hydrophobic cyano group side base polymerization bonding agent, molecule is one-dimensional linear structure, and pressrun is not high; Kodak US2006-7-2711/494,235 introduce a kind of solvent resistant polymkeric substance containing hydrophilic group and cyano group side base, containing allyl ester side chain, that condensation reaction under alkali effect forms by carboxyl side group and allyl halide, but side reaction by-products is more, aftertreatment bothers, and ester group still not resistance to print.
At present, improve the performance exempting to process heat-sensitive CTP plate further, the resistance to print ability particularly improving plate is the focus of thermal CTP plate material exploitation.
Improve and exempt from the resistance to print ability of process heat-sensitive CTP plate plate, need the solvent resistance improving plate.Plate solvent resistant refers to the corrosion of the organic solvent in the resistance to various printing chemicals of printing plate, as use in printing flushing oil, fountain solution, gum-solution, forme preserving agent, plate cleaners, ink particularly UV ink-washing oil corrosion.
CTP version plate resistance to print ability and plate solvent resistance have certain relevance, and in general, the good plate of solvent resistance has higher wearing quality, can obtain higher pressrun.
The method improving the solvent resistance of heat-sensitive CTP plate plate and Nai Yin ability is a lot, and wherein one of most important method is exactly the exploitation of printing plate organism particularly functional film-forming resin.Open source information according to the patent US6294311 of Shimazu: carboxyl acrylic resin, vinyl acetate/crotonates (trans-2-butene acid esters)/vinyl neodecanoate multipolymer, styrene maleic anhydride copolymer, phenolics, maleated wood rosin and their composition, have solvent resistant effect, the maleimide of especially N-replacement, methyl acrylamide, polyvinyl acetaldehyde polymkeric substance can improve the print journey of forme; Kodak patent CN101321632A is disclosed introduces phosphoric acid or diamantane side base at polymkeric substance, improves chemical-resistant and the pressrun of plate; Kodak proposes at WO2004/033206, introduces barbiturates group in macromolecule resin side chain, obviously can improve solvent resistance and the wearing quality of plate coating, improves plate pressrun; Kodak discloses a kind of QHB phenol-formaldehyde resin modified in WO2004/033206, with iso-cytosine (2-amino-4-hydroxy pyrimidine) and isocyanate-modified phenolics, form strong polarity tetrahydrochysene bonding structure, be used in multilayer heat-sensitive version upper strata i.e. the second polymer layer, to improve the wearing quality of plate; At Kodak patent US2006,045648 disclose a kind of containing acid anhydride-based polymer solvent resistant plate, its announce the most useful anhydride group be maleic anhydride and derivant thereof; Agfa Corp. EP [31] 02102446.8 discloses a kind of method of modifying by phenolic hydroxyl group distant pawl group, phenolics being carried out to diazo salt grafting, form azo-aromatic yl group (-N=N-Q group, Q is aromatic group), improve chemical resistance of coating, improve plate pressrun; Fujiphoto [32] 2004.3.11 [33] JP [31] 2004-069478 proposes the temperature-sensitive version resin that main chain has phenol skeleton and a urea key (-NHCONH-) and has solvent resistance, improves the pressrun of printing plate; A kind of temperature-sensitive platemaking technology is disclosed at European patent EP-A-1101607, a kind of plate solvent resistant technology is described in this section of patent, in plate coating, with the addition of a kind of acidic cellulosic polymers, improve the solvent resistance of plate coating, this temperature-sensitive version can resist ink and fountain solution to the erosion of plate rete, has excellent pressrun.
The method of above-mentioned raising heat-sensitive CTP plate plate print ability, all by the particularly functional film-forming resin realization of exploitation printing plate organism.
We know, macromolecule resin is divided into linear structure and reticulate texture, and in general, linear structure resin can be dissolved in solvent, and cancellated macromolecule resin generally can only can not by dissolution with solvents by solvent swell.So reticular polymer resin has good wearing quality.
Exempting to process heat-sensitive CTP plate production process is generally that heat-sensitive composition is coated on supporter as on aluminum substrate, so be difficult to realize adding the reticular polymer resin being difficult to dissolve in heat-sensitive composition to obtain good wearing quality to improve plate pressrun by the mode of dip-coating, spraying or extrusion coated as a solution.
Summary of the invention
For the problems referred to above, the present invention devises a kind of temperature-sensitive version exempting to process thermal CTP plate material negative graph photosensitive composition and make of it.Negative graph photosensitive composition comprises discrete receive micron particles, two urea ketone performed polymers, polyfunctional monomer, thermal polymerization, infrared absorbing agents and organic metal promoter.Plate has brand-new multiple temperature-sensitive imaging mechanism, micron particles hot melt thermoplastic, the linear thermal polymerization of free radical and polyurethane mesh heat cross-linking can be received in realization, multiple temperature-sensitive imaging mechanism plate is had light sensitivity is high, site is Well-recovered, the advantage of high pressrun.After with infrared laser scanning imagery, it is oleophylic that micron particles hot melt thermoplastic of receiving destroys oil-in-water Structure Transformation, the linear thermal polymerization of free radical simultaneously and polyurethane mesh heat cross-linking make coating molecule amount sharply become large, make coating more firm, the coating after LASER HEAT exposure is difficult to be removed by damping water and ink; The unnecessary coating at unexposed blank position is on the printer by what remove under the effect of damping water and ink, and walked by transferring paper tape after unnecessary coating removal, blank position is hydrophilic aluminum substrate.Strong polarity ammonia ester bond cross-linked network makes plate can obtain the pressrun of superelevation.This mode can directly be printed on the machine without any need for washing processing step, and can obtain very high pressrun, achieves the environmental protection object of lithography process without emissions.
The present invention can solve the existing shortcoming exempting to process plate solvent resistant ability and the Nai Yin ability existed in heat-sensitive CTP plate technology, is particularly difficult to realize obtaining good wearing quality to improve the problem of plate pressrun by adding the reticular polymer resin being difficult to dissolve in heat-sensitive composition.
Negative graph photosensitive composition comprises discrete receive micron particles, two urea ketone performed polymers, polyfunctional monomer, thermal polymerization, infrared absorbing agents and organic metal promoter.Plate has brand-new multiple temperature-sensitive imaging mechanism, micron particles hot melt thermoplastic, the linear thermal polymerization of free radical and polyurethane mesh heat cross-linking can be received in realization, multiple temperature-sensitive imaging mechanism plate is had light sensitivity is high, site is Well-recovered, the advantage of high pressrun.For achieving the above object, the present invention adopts following technical scheme: negative graph photosensitive composition comprises discrete receive micron particles, two urea ketone performed polymers, polyfunctional monomer, thermal polymerization, infrared absorbing agents and organic metal promoter.Plate has brand-new multiple temperature-sensitive imaging mechanism:
A, plate have hot melt thermoplastic imaging capability: discrete micron particles of receiving is that water wettability thermoplastic hot melt receives micron particles structure, it has ultra micro and receives the same Strange properties of micron particles, and namely the character of its optics, calorifics, electricity, magnetics, mechanics and chemical aspect will have significant difference with comparing during bulk solid.With regard to fusing point, it is few that ultra micro receives each particle composed atom of micron particles, and surface atom is in destabilization state, and the amplitude that its lattice surface is shaken is comparatively large, so have higher surface energy, causes the distinctive thermal property of ultramicron: fusing point declines.The micron particles of receiving of the present invention's design can realize the imaging of hot melt thermoplastic under infrared laser heat effect.
B, plate have the ability of free radical thermal polymerization: laser energy is passed to thermal polymerization by infrared absorbing agents by the heat of infrared laser, thermal polymerization discharges competent primary free radical, primary group of free radicals causes the unsaturated double-bond in polyfunctional monomer and two urea ketone performed polymers, realizes free radical linear polymerization.
C, plate has the crosslinked ability of weblike heat: the heat of infrared laser makes two urea ketone in two urea ketone performed polymers produce thermofission by the laser energy that infrared absorbing agents transmits, produce active isocyanate base (-NCO), polyurethane reaction is there is with the branched hydroxy group (-OH) received in micron particles in active isocyanate base (-NCO) under the catalytic action of organic metal promoter, form the ammonia ester bond (-NHCOO) of strong polarity, polyurethane mesh heat cross-linking is realized while realizing free radical linear polymerization, strong polarity ammonia ester bond has very high wearing quality, ammonia ester bond cross-linked network makes plate can obtain the pressrun of superelevation.
After infrared laser scanning imagery, it is oleophylic that micron particles hot melt thermoplastic of receiving destroys oil-in-water Structure Transformation, the linear thermal polymerization of free radical simultaneously and polyurethane mesh heat cross-linking make coating molecule amount sharply become large, and make coating more firm, the coating after LASER HEAT exposure is difficult to be removed by damping water and ink; The unnecessary coating at unexposed blank position is on the printer by what remove under the effect of damping water and ink, and walked by transferring paper tape after unnecessary coating removal, blank position is hydrophilic aluminum substrate.Strong polarity ammonia ester bond cross-linked network makes plate can obtain the pressrun of superelevation.This mode can directly be printed on the machine without any need for washing processing step, and can obtain very high pressrun, achieves the environmental protection object of lithography process without emissions.
Below the present invention is elaborated:
The temperature-sensitive plate that the present invention devises a kind of negative graph photosensitive composition and makes by said composition.Negative graph photosensitive composition comprises discrete receive micron particles, two urea ketone performed polymers, polyfunctional monomer, thermal polymerization, infrared absorbing agents and organic metal promoter.Plate has brand-new multiple temperature-sensitive imaging mechanism, micron particles hot melt thermoplastic, the linear thermal polymerization of free radical and polyurethane mesh heat cross-linking can realized receiving, strong polarity ammonia ester bond has very high wearing quality, ammonia ester bond cross-linked network makes plate can obtain the pressrun of superelevation, version could directly be printed on the machine, and realizes environmental protection.
First discrete micron particles of receiving in negative graph photosensitive composition is described.
Design a kind of Thermal sensitive plate, first it is considered that the heat susceptible coating of plate, in heat susceptible coating, need a kind of important cementing agent and functional film-forming resin, resin can after guarantee coating fluid drying film forming, heat susceptible coating is attached on support.Cementing agent can be solution state, also can be emulsion state.Discrete micron particles of receiving in negative graph photosensitive composition of the present invention is exactly this type of cementing agent.
Discrete micron particles grain diameter of receiving in negative graph photosensitive composition of the present invention is 50-300nm, has following structure:
R1, R2, R4 are H atom or methyl, and R3 is CH2CH2OH or CH2CH2CH2OH, R5 be COO (CH2CH2) nH or COOCH2CH2NHCOO (CH2CH2) nH, n is the integer of 20-60;
A, b, c, d are the percent by weight of corresponding copolymerization units, and a proportion is 40-70%, b proportion be 10-30%, c proportion be 10-30%, d proportion is 10-30%.
Great majority are exempted from the discrete micron particles bonding agent of receiving of chemical treatment heat-sensitive CTP plate and are all devised thermoplastic styrene structural unit.Discrete type of the present invention receives micron particles also containing thermoplastic styrene structural unit.As everyone knows, styrol structural unit has good 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 bonding agent, arrange more tight between molecule, thermal imagery part is more firm, can increase the advantage of plate pressrun.Styrene content in the copolymer directly affects glass transition temperature and the thermoplasticity of polymkeric substance.Synthesize multiple copolymer of the present invention, styrenic interpolymerized units in the copolymer weight percent content is 40-70%.
Design a kind of CTP version bonding agent, select outstanding hydrophobic segment to be necessary.Cyano group is more outstanding hydrophobic group.Discrete type of the present invention is received micron particles and is introduced hydrophobic side chain cyano group, after multipolymer introduces hydrophobic side chain cyano group, as bonding agent thermoplastic fusion of imaging part, has good pliability, drug resistance and hydrophobic nature.The method that multiple copolymer of the present invention introduces hydrophobic side chain radical nitrile is in copolymerization component, devise the vinyl component structural unit of side chain containing base nitrile, preferred vinyl cyanide or methacrylonitrile or their potpourri.Synthesize multiple copolymer of the present invention, (methyl) acrylonitrile compolymer unit weight percent content in multiple copolymer is 10-30%.
The plate of the present invention's design has the crosslinked ability of weblike heat, the heat of infrared laser makes two urea ketone in two urea ketone performed polymers produce thermofission by the laser energy that infrared absorbing agents transmits, produce active isocyanate base (-NCO), polyurethane reaction is there is with the branched hydroxy group (-OH) received in micron particles in active isocyanate base (-NCO) under the catalytic action of organic metal promoter, form the ammonia ester bond (-NHCOO) of strong polarity, while realizing free radical linear polymerization, realize polyurethane mesh heat cross-linking.The present invention introduces branched hydroxy group discrete receiving in micron particles macromolecule resin structural chain, select the acrylic monomer of hydroxyl as copolymerization units, the acrylic monomer of hydroxyl has acrylic acid-2-hydroxyl ethyl ester, 2-hydroxypropyl acrylate (HPA), methacrylic acid-2-hydroxyl ethyl ester (HEMA), Hydroxypropyl methacrylate (HPMA) etc., and acrylic monomer copolymerization units weight percent content in multiple copolymer of hydroxyl is 10-30%.
As exempting from chemical treatment CTP version emulsion binding agent, discrete type receives micron particles, and to contain self-emulsifying structural unit relatively good, polymkeric substance can realize emulsification not having the polyethers emulsification group by self under additional emulsifying agent existent condition, the emulsion particle of synthesis is more homogeneous, mellow and full than outer emulsification emulsion particle, and stability is better.Discrete micron particles of receiving of the present invention devises polyethers self-emulsifying structural unit in copolymerization component, comprises esterification branched polyether and ammonia esterification branched polyether, object lesson following (being not limited only to this):
A1:
A2:
Polyethers self-emulsifying structure copolymerization units weight percent content in multiple copolymer is 10-30%.
Synthesize discrete micron particles of receiving of the present invention and adopt the method for emulsion copolymerization, the optional random copolymerization of copolyreaction or block copolymerization, preferred random copolymerization.The initiating agent of polymerization comprises superoxide as di-tert-butyl peroxide, benzoyl peroxide, and persulfate is as potassium persulfate, Ammonium Persulfate 98.5, and azo-compound is as azoisobutyronitrile etc.Copolymerization mode adopts emulsion polymerization.
Available reaction dissolvent has water, methyl alcohol, ethanol, n-propanol, isopropyl alcohol, butanols, acetone, MEK, cyclohexanone, ethyl acetate, butyl acetate, tetrahydrofuran, 1, 4-dioxane, N, dinethylformamide, dimethyl acetamide acetone, methyl ethyl ketone, cyclohexane, ethylene dichloride, toluene, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, glycol dimethyl ether, propylene glycol monomethyl ether, propylene-glycol ethyl ether, diacetone, diacetone alcohol, 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, , dimethyl sulfoxide, methyl lactate and ethyl lactate etc., or their potpourri.Preferably adopt the potpourri of alcohol and water, the potpourri of preferred n-propanol-water or isopropanol-water.The preferred 40-100 DEG C of emulsion copolymerization temperature of reaction, optimum is 60-90 DEG C.
Synthesize discrete micron particles of receiving of the present invention, the mode that feed way adopts part material to drip, the discrete particle size receiving micron particles can by changing reaction system concentration and time for adding control, the discrete diameter receiving micron particles diminishes along with the minimizing of reaction system concentration and the increase of time for adding, can be controlled the discrete particle size receiving micron particles at nano-micro level by adjustment reaction system concentration and time for adding.Discrete micron particles grain diameter of receiving in negative graph photosensitive composition of the present invention is 50-300nm.
Discrete micron particles weight-average molecular weight of receiving of the present invention is 40000-10000.Glass transition temperature is 110-130 DEG C.
The discrete micron particles of receiving of the present invention's design accounts for the 30-70% of constituent solid amount, is preferably 40-60%.
First secondly the two urea ketone performed polymers described in negative graph photosensitive composition are described.
The plate that the present invention designs the present invention's design has the crosslinked ability of weblike heat, the heat of infrared laser makes two urea ketone in two urea ketone performed polymers produce thermofission by the laser energy that infrared absorbing agents (dyestuff) transmits, produce active isocyanate base (-NCO), polyurethane reaction is there is with the branched hydroxy group (-OH) received in micron particles in active isocyanate base (-NCO) under the catalytic action of organic metal promoter, form the ammonia ester bond (-NHCOO) of strong polarity, while realizing free radical linear polymerization, realize polyurethane mesh heat cross-linking.
Two urea ketone performed polymers in negative graph photosensitive composition of the present invention, have following general structure:
Wherein, R is:
Laser pyrolysis mechanism signal chemical formula is as follows:
Two urea ketone are by the dimer of two isocyanate group, and these two isocyanate group can be provided by two kinds of different structure isocyanates (-R1-NCO ,-R2-NCO), also can be that the mutually isostructural isocyanates (-RNCO) of one provides.Two isocyanate group that the present invention synthesizes two urea ketone are selected and are provided by the mutually isostructural isocyanates of one-(RNCO).The two urea ketone structural symmetry providing isocyanate group to synthesize by a kind of mutually isostructural isocyanates, ordinary temperature stability is good, and under laser action, to go out active isocyanate (-NCO) base rapid for pyrolytic.
The b bis-urea ketone performed polymer of the present invention's design contains unsaturated double-bond, and unsaturated double-bond is connected with isocyanate group by hydroxyl, so the isocyanates selected by the present invention is diisocyanate.Diisocyanate comprises aromatic diisocyanates toluene diisocyanate (TDI) and methyl diphenylene diisocyanate (MDI), PPDI (PPDI), naphthalene diisocyanate (NDI), dimethyl diphenyl diisocyanate (TODI); Fatty and alicyclic isomeride is 1,6-hexamethylene diisocyanate (HDI), 1-isocyanates-3-isocyanates methylene-3,5,5-Trimethyl-cyclohexyl (isoflurane chalcone diisocyanate, IPDI), 4,4'-hexylmethane (H12MDI), XDI (XDI), cyclohexane diisocyanate (CHDI), tetramethylxylylene diisocyanate (TMXDI), 1,3-bis-(isocyanatomethyl) cyclohexane (H6XDI) etc.The diisocyanate that b bis-urea ketone performed polymer in synthesis the present invention is selected is aromatic diisocyanate or the diisocyanate containing cyclohexyl.Consider that the ordinary temperature stability of two urea ketone performed polymers is good, laser pyrolysis, the diisocyanate that the present invention selects is methyl diphenylene diisocyanate (MDI), 4,4'-hexylmethane (H12MDI), XDI (XDI), toluene diisocyanate (TDI), naphthalene diisocyanate (NDI).
The unsaturated double-bond that the b bis-urea ketone performed polymer of the present invention's design contains is connected with isocyanate group by hydroxyl, and the unsaturated double-bond monomer of hydroxyl has acrylic acid-2-hydroxyl ethyl ester, 2-hydroxypropyl acrylate (HPA), 2-hydroxyethyl methacry-late (HEMA), Hydroxypropyl methacrylate (HPMA), pentaerythritol triacrylate (PETA) etc.Consider that the ordinary temperature stability of the activity of unsaturated double-bond and two urea ketone performed polymers is good, laser pyrolysis, the unsaturated double-bond monomer of the hydroxyl that the present invention selects is 2-hydroxyethyl methacry-late (HEMA) and pentaerythritol triacrylate (PETA).
The b bis-urea ketone performed polymer of the present invention's design accounts for the 10-50% of constituent solid amount, is preferably 20-40%.
The polyfunctional monomer of photopolymerization of the present invention, there is diacrylate, 1,6-hexanediyl ester, pentaerythritol triacrylate and tetraacrylate, 1,3,5 one three one (2 one acrylyl oxy-ethyl) isocyanuric acid ester, hydroxypropyl glycerine base triacrylate, hydroxyethyl trimethylolpropane triacrylate, polyethylene glycol dimethacrylate etc.Polyfunctional monomer accounts for 10 ~ 30% of film dry weight for good in light sensitive layer, and preferably 10% ~ 20%.
Component in temperature-sensitive version negative composition of the present invention is described in detail in detail: thermal polymerization below.
Temperature-sensitive version of the present invention is polymerism plate, plate has the ability of free radical thermal polymerization, laser energy is passed to thermal polymerization by infrared absorbing agents by the heat of infrared laser, thermal polymerization discharges competent primary free radical, primary group of free radicals causes the unsaturated double-bond in polyfunctional monomer and two urea ketone performed polymers, realizes free radical linear polymerization.
Thermal polymerization decomposes in the present invention generates primary group of free radicals, causes unsaturated double-bond generation free radical polymerization.The thermal polymerization kind that can cause free radical polymerization has a lot, comprises superoxide as hydrogen peroxide, ammonium persulfate, potassium persulfate, benzoyl peroxide, the benzoyl peroxide tert-butyl ester, methyl ethyl ketone peroxide etc.; Azo compound is as azoisobutyronitrile, ABVN, azo-bis-iso-dimethyl, band carboxyl, sulfonic azo-compound, azo diisobutyl amidine hydrochloride etc.; Salt is as salt compounded of iodine, sulfosalt etc.; And contain triaizine compounds of halogen substiuted etc.Ordinary temperature stability and the LASER HEAT of investigating them decompose sensitivity, and in them, halogen substiuted triaizine compounds becomes preferred.Thermal polymerization accounts for the 1-20% of constituent solid amount, is preferably 5-15%.
Component in temperature-sensitive version negative composition of the present invention is described in detail in detail: infrared absorbing agents below.
Component in temperature-sensitive version composition of the present invention: infrared absorbing agents mainly plays energy trasfer, laser energy is passed to thermal polymerization by infrared absorbing agents by the heat of infrared laser, thermal polymerization discharges competent primary free radical, primary group of free radicals causes the unsaturated double-bond in polyfunctional monomer and two urea ketone performed polymers, realizes free radical linear polymerization; Simultaneously, the heat of infrared laser makes two urea ketone in two urea ketone performed polymers produce thermofission by the laser energy that infrared absorbing agents transmits, produce active isocyanate base (-NCO), polyurethane reaction is there is with the discrete branched hydroxy group (-OH) receiving micron particles in active isocyanate base (-NCO) under the catalytic action of e organic metal promoter, form ammonia ester bond (-NHCOO), while realizing free radical linear polymerization, realize polyurethane mesh heat cross-linking.
Contained by negative graph photosensitive composition, the maximum absorption wavelength scope of infrared absorbing compounds 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 absorbing agents is the cyanine dyes that absorption maximum ranges preferably from 750-850nm, infrared absorbing agents accounts for 1 ~ 20% of film dry weight for good in light sensitive layer, and preferably 5% ~ 15%.
Component contained by negative graph photosensitive composition of the present invention is described in detail in detail: organic metal promoter below.
Temperature-sensitive version of the present invention has the feature of polyurethane heat cross-linking, the heat of infrared laser makes two urea ketone in two urea ketone performed polymers produce thermofission by the laser energy that infrared absorbing agents transmits, produce active isocyanate base (-NCO), polyurethane reaction is there is with the discrete branched hydroxy group (-OH) receiving micron particles in active isocyanate base (-NCO) under the catalytic action of e organic metal promoter, form ammonia ester bond (-NHCOO), while realizing free radical linear polymerization, realize polyurethane mesh heat cross-linking.
Polyurethane reaction generally needs catalyzer, can promote that the catalyzer of polyurethane reaction has a lot, and Polyurethane catalyzer can be divided into two large class, amines and organometallicss.Aminated compounds is as triethylenediamine (TEDA), dimethyl cyclohexyl amine (DMCHA), dimethylethanolamine (DMEA), tetramethyl butane diamine (TMBDA), dimethylamino sulfuric ether (A-99) benzyl dimethylamine (BDMA) etc.; Organometallics is as organometallics of mercury, lead, tin, bismuth, zinc, iron etc.Component in temperature-sensitive version composition of the present invention: organic metal promoter selects stable, efficient organic metal tin compound, as lauric acid diisobutyl tin, stannous octoate etc.Organic metal tin compound accounts for 0.5 ~ 5% of film dry weight for good in light sensitive layer, and preferably 1% ~ 3%.
The support of temperature-sensitive version of the present invention is finally described in detail in detail.
Temperature-sensitive version 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 0.3-0.6um.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 lose be limited 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 electrolytic solution used can be acid, alkali or the aqueous solution of salt or the aqueous solution containing organic solvent.Wherein, electrolytic solution 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 silicate etc. of 1%-30%, at the temperature of 20-80 DEG C, carries out the chemical corrosion 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 electrolytic solution 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 adsorptive power 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.
Photosensitive 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 susceptible coating, the photosensitive liquid solvent of preparation heat susceptible coating comprises: acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, glycol dimethyl ether, propylene glycol monomethyl ether, propylene-glycol ethyl ether, diacetone, cyclohexanone, diacetone alcohol, 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, dimethyl 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, nitroxyl 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 susceptible coating contains layer colorant.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 measuring equipment 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 colorant.It comprises: methyl violet, ethyl violet, crystal violet, purple in crystallization, Victoria blue, glossy dark green, oil blue, oil yellow, rhodamine B, methyl violet rowland, malachite green, methylene blue, triazines etc.
Heat susceptible coating contains surfactant, can select non-ionic surfactant, amphoteric surfactant, silicon-containing surfactant, fluorochemical 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 susceptible coating is coated with layer protective layer, prevents the performance of the pollutant effect heat susceptible coating in the oxygen that exists in air or other environment.As the material for the protection of layer, the water miscible polymkeric substance of preferred tool, as poly-(vinyl alcohol), polyvinylpyrrolidone, acid cellulose derivant, gelatin, gum arabic and poly-(allyl phenol etc.These materials can obtain as the principal ingredient of protective seam and refuse oxygen and development removeability very well.For the object lesson of polyvinyl alcohol (PVA), can be exemplified as 71-100% hydrolysis and molecular weight is the compound of 300 1 2400.Object lesson has: PVA-105, PVA-110, PVA-117, PVA mono-117H.PVA 1, PVA mono-124.PVA mono-124H.PVA mono-CS.PVA mono-CST, PVA mono-HC.PVA mono-203, PVA mono-204, PVA mono-205, PVA 1 210, PVA 1, PVA mono-220, PVA 1 224, PVA mono-217EE, PVA mono-217E, PVA mono-220E.PVA mono-224E, PVA 1, PVA mono-420, PVA mono-613 etc.The coating weight of protective seam 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.
Embodiment
Here is synthesis example of the present invention, but the present invention is not limited to following example.
Starting material can obtain from following company: styrene St: Han Dynasty in Shandong Province honor Energy Science Co., Ltd; Methacrylonitrile MAN, vinyl cyanide AN: Tianjin chemical reagent two factory; Hydroxyethyl methylacrylate HEMA, hydroxy-ethyl acrylate HEA, hydroxy propyl methacrylate HPMA, hydroxypropyl acrylate HPA: Mitsubishi Li Yang Co., Ltd.; Example compound A1, A2: SIGMA company of Britain; Isopropyl alcohol: Yangzhou becomes space chemical industry; Azo-bis-isobutyl cyanide: the gloomy chemistry of good fortune; Benzoyl peroxide BPO: Laiwu health novel agent.
Part I: discrete submicron emulsion particle (code name P) of receiving synthesizes example P1-P10
Embodiment 1(emulsion particle P01)
Temperature control heating is with at 1000ml, mechanical raking, 300g isopropyl alcohol is added in the four-hole boiling flask of condensing reflux and nitrogen protection device, 100g deionized water, 10g(10 % by weight) example compound A1 (n about 60), heating stirs, 70g,(70 % by weight is dripped at 80 DEG C) St (styrene), 10g (10 % by weight) AN (vinyl cyanide), 10g(10 % by weight) HEMA hydroxyethyl methylacrylate, 0.7gAIBN (azoisobutyronitrile), time for adding 1 hour, 0.3gAIBN (azoisobutyronitrile) is added after reacting 7.5 hours again, continue to react again after 12 hours and terminate.
Solid content is 25%, GPC molecular weight is 93600, and particle diameter is 200nm.
Embodiment 2(emulsion particle P02)
Temperature control heating is with at 1000ml, mechanical raking, 357g isopropyl alcohol is added in the four-hole boiling flask of condensing reflux and nitrogen protection device, 119g deionized water, 10g(10 % by weight) example compound A2 (n about 50), heating stirs, 60g,(60 % by weight is dripped at 60 DEG C) St (styrene), 20g (20 % by weight) AN (vinyl cyanide), 10g(10 % by weight) HEMA hydroxyethyl methylacrylate, 0.7gAIBN (azoisobutyronitrile), time for adding 1.5 hours, 0.3gAIBN (azoisobutyronitrile) is added after reacting 7.5 hours again, continue to react again after 12 hours and terminate.
Solid content (solute/solvent) is 21%, GPC molecular weight is 76800, and particle diameter is 150nm.
Embodiment 03(emulsion particle P03)
Temperature control heating is with at 1000ml, mechanical raking, 417g isopropyl alcohol is added in the four-hole boiling flask of condensing reflux and nitrogen protection device, 139g deionized water, 10g(10 % by weight) example compound A1 (n about 40), heating stirs, 50g,(50 % by weight is dripped at 60 DEG C) St (styrene), 30g (30 % by weight) AN (vinyl cyanide), 10g(10 % by weight) HEA hydroxy-ethyl acrylate, 0.7gAIBN (azoisobutyronitrile), time for adding 2.0 hours, 0.3gAIBN (azoisobutyronitrile) is added after reacting 7.5 hours again, continue to react again after 12 hours and terminate.
Solid content is 18%, GPC molecular weight is 63700, and particle diameter is 100nm.
Embodiment 04(emulsion particle P04)
Temperature control heating is with at 1000ml, mechanical raking, 500g isopropyl alcohol is added in the four-hole boiling flask of condensing reflux and nitrogen protection device, 167g deionized water, 10g(10 % by weight) example compound A2 (n about 20), heating stirs, 40g,(40 % by weight is dripped at 60 DEG C) St (styrene), 10g (10 % by weight) AN (vinyl cyanide), 20g(20 % by weight) HEA hydroxy-ethyl acrylate, 0.7gAIBN (azoisobutyronitrile), time for adding 2.5 hours, 0.3gAIBN (azoisobutyronitrile) is added after reacting 7.5 hours again, continue to react again after 12 hours and terminate.
Solid content is 15%, GPC molecular weight is 40500, and particle diameter is 50nm.
Embodiment 05(emulsion particle P05)
Temperature control heating is with at 1000ml, mechanical raking, 250g isopropyl alcohol is added in the four-hole boiling flask of condensing reflux and nitrogen protection device, 83.3g deionized water, 10g(10 % by weight) example compound A1 (n about 50), heating stirs, 60g,(60 % by weight is dripped at 90 DEG C) St (styrene), 10g (10 % by weight) MAN (methacrylonitrile), 20g(20 % by weight) HEPA hydroxy propyl methacrylate, 0.7g benzoyl peroxide BPO, time for adding 0.5 hour, 0.3g benzoyl peroxide BPO is added after reacting 7.5 hours again, continue to react again after 12 hours and terminate.
Solid content is 30%, GPC molecular weight is 102400, and particle diameter is 300nm.
Embodiment 06(emulsion particle P06)
Temperature control heating is with at 1000ml, mechanical raking, 268g isopropyl alcohol is added in the four-hole boiling flask of condensing reflux and nitrogen protection device, 89.3g deionized water, 10g(10 % by weight) example compound A2 (n about 40), heating stirs, 50g,(50 % by weight is dripped at 85 DEG C) St (styrene), 10g (10 % by weight) MAN (methacrylonitrile), 30g(30 % by weight) HPMA methacrylic acid hydroxypropyl ethyl ester, 0.7g benzoyl peroxide BPO, time for adding 45 minutes, 0.3g benzoyl peroxide BPO is added after reacting 7.5 hours again, continue to react again after 12 hours and terminate.
Solid content is 28%, GPC molecular weight is 97500, and particle diameter is 250nm.
Embodiment 07(emulsion particle P07)
Temperature control heating is with at 1000ml, mechanical raking, 312.5g isopropyl alcohol is added in the four-hole boiling flask of condensing reflux and nitrogen protection device, 104.1g deionized water, 30g(30 % by weight) example compound A1 (n about 20), heating stirs, 40g,(40 % by weight is dripped at 80 DEG C) St (styrene), 20g (20 % by weight) MAN (methacrylonitrile), 10g(10 % by weight) HPA hydroxypropyl acrylate, 0.7gAIBN (azoisobutyronitrile), time for adding 1 hour 20 minutes, 0.3gAIBN (azoisobutyronitrile) is added after reacting 7.5 hours again, continue to react again after 12 hours and terminate.
Solid content is 24%, GPC molecular weight is 91300, and particle diameter is 180nm.
Embodiment 08(emulsion particle P08)
Temperature control heating is with at 1000ml, mechanical raking, 441g isopropyl alcohol is added in the four-hole boiling flask of condensing reflux and nitrogen protection device, 147g deionized water, 20g(20 % by weight) example compound A2 (n about 60), heating stirs, 60g,(60 % by weight is dripped at 65 DEG C) St (styrene), 10g (10 % by weight) AN (vinyl cyanide), 10g(10 % by weight) HPA hydroxypropyl acrylate, 0.7gAIBN (azoisobutyronitrile), time for adding 2.5 hours, 0.3gAIBN (azoisobutyronitrile) is added after reacting 7.5 hours again, continue to react again after 12 hours and terminate.
Solid content is 17%, GPC molecular weight is 56400, and particle diameter is 70nm.
Embodiment 09(emulsion particle P09)
Temperature control heating is with at 1000ml, mechanical raking, 375g isopropyl alcohol is added in the four-hole boiling flask of condensing reflux and nitrogen protection device, 125g deionized water, 30g(30 % by weight) example compound A1 (n about 30), heating stirs, 50g,(50 % by weight is dripped at 70 DEG C) St (styrene), 10g (10 % by weight) AN (vinyl cyanide), 10g(10 % by weight) HEMA hydroxyethyl methylacrylate, 0.7gAIBN (azoisobutyronitrile), time for adding 2 hours 15 minutes, 0.3gAIBN (azoisobutyronitrile) is added after reacting 7.5 hours again, continue to react again after 12 hours and terminate.
Solid content is 20%, GPC molecular weight is 68700, and particle diameter is 90nm.
Embodiment 10(emulsion particle P10)
Temperature control heating is with at 1000ml, mechanical raking, 326g isopropyl alcohol is added in the four-hole boiling flask of condensing reflux and nitrogen protection device, 108.7g deionized water, 10g(10 % by weight) example compound A2 (n about 60), heating stirs, 40g,(40 % by weight is dripped at 80 DEG C) St (styrene), 30g (30 % by weight) AN (vinyl cyanide), 10g(10 % by weight) HEA hydroxy-ethyl acrylate, 0.7gAIBN (azoisobutyronitrile), time for adding 1 hour, 0.3gAIBN (azoisobutyronitrile) is added after reacting 7.5 hours again, continue to react again after 12 hours and terminate.
Solid content is 23%, GPC molecular weight is 85400, and particle diameter is 130nm.
Comparative example 1-5(synthesizes similar Ai Kefa emulsion particle A1-A5):
Introduce a kind of semicontinuous emulsion method according to Ai Kefa patent EP2006-5-2406114475.4 and manufacture styrene, acrylonitrile emulsion thermoplastic granulates, can hot melt be realized, but not containing self-emulsifying hydrophilic radical, plastic cement particulate body structure:
Synthesize similar emulsion particle A1-A5.
Basic operation: be with at 1000ml in the four-hole boiling flask of temperature control heating, mechanical raking, condensing reflux and nitrogen protection device and add 250g n-propanol, 75g deionized water, 5g lauryl sodium sulfate; 60g,(60 % by weight is dripped at 80 DEG C) ST (styrene), 40g (40 % by weight) AN (vinyl cyanide), 0.7gAIBN (azoisobutyronitrile); time for adding 2.5 hours; add 0.3gAIBN (azoisobutyronitrile) after reacting 7.5 hours again, continue to react again after 12 hours and terminate.
Solid content is 23.5%, GPC molecular weight is 80000, and particle diameter is 55nm.
Change reaction density, time for adding changes particle diameter, molecular weight, synthesize similar Ai Kefa emulsion particle A1-A5, performance sees attached list 1.
Comparative example 6-10(synthesizes similar Kodak emulsion particle K1-K5):
A kind of self-emulsifying bonding agent comprising polyalkylene oxide hydrocarbon segment and the polymerization of hydrophobic cyano group side base is introduced, plastic cement particulate body structure according to Kodak patent US2005-8-311/196:
Synthesize similar emulsion particle K1-K5.
Basic operation: be with at 1000ml in the four-hole boiling flask of temperature control heating, mechanical raking, condensing reflux and nitrogen protection device and add 250g n-propanol, 75g deionized water; drip 20,g(0 % by weight at 80 DEG C) ST (styrene), 70g (70 % by weight) AN (vinyl cyanide), 20g0.7g (20 % by weight) PEGMA (polyethoxy methacrylate), AIBN (azoisobutyronitrile); time for adding 2.5 hours; add 0.3gAIBN (azoisobutyronitrile) after reacting 7.5 hours again, continue to react again after 12 hours and terminate.
Solid content is 23.5%, GPC molecular weight is 80000, and particle diameter is 75nm.
Change reaction density, time for adding changes particle diameter, molecular weight, synthesize similar Kodak emulsion particle K1-K5, performance sees attached list 1.
B: two urea ketone performed polymers: synthesis example b1-b5
Starting material can obtain from following company: pentaerythritol triacrylate PETA: U.S. Sartomer Sardomer, SR444; 2-hydroxyethyl methacry-late: Mitsubishi Li Yang Co., Ltd.; Ditolyl methane diisocyanate MDI: Mitsui chemistry; Toluene diisocyanate TDI: Japanese polyurethane industrial group; XDI XDI: Japanese Wu Tian pharmaceutical industries company, takenato; Naphthalene-1,5-diisocyanate NDI: Mitsui Dong Ya KCC; Dicyclohexyl methyl hydride diisocyanate HMDI:Bayer, DeStodurw; MEK MEK: Japan improves petrochemical industry.
B compou nd synthesis example b1:
Temperature control heating is with at 2000ml, mechanical raking, 298.0g pentaerythritol triacrylate PETA is added in the four-hole boiling flask of condensing reflux and nitrogen protection device, g MEK MEK, 1.0g dibutyl tin laurate, nitrogen protection, be heated to the 500.5g ditolyl methane diisocyanate MDI that 60 DEG C drip melting, time for adding 30 minutes, react and drip 130.1g 2-hydroxyethyl methacry-late after 2 hours, time for adding is 30 minutes, react 2 hours again, add 232.1g MEK, react 48 hours under ice-water bath, until disappeared by peak, infrared spectrum detection of active isocyanate group 2275 place, obtain the MEK solution that solid content is the compound b1 of 80%.
B compou nd synthesis example b2:
Temperature control heating is with at 1000ml, mechanical raking, 298.0g pentaerythritol triacrylate PETA is added in the four-hole boiling flask of condensing reflux and nitrogen protection device, g MEK MEK, 1.0g dibutyl tin laurate, nitrogen protection, be heated to 60 DEG C and drip 348.3g toluene diisocyanate TDI, time for adding 30 minutes, react and drip 130.1g 2-hydroxyethyl methacry-late after 2 hours, time for adding is 30 minutes, react 2 hours again, add 194.1g MEK, react 48 hours under ice-water bath, until disappeared by peak, infrared spectrum detection of active isocyanate group 2275 place, obtain the MEK solution that solid content is the compound b2 of 80%.
B compou nd synthesis example b3:
Temperature control heating is with at 1000ml, mechanical raking, 298.0g pentaerythritol triacrylate PETA is added in the four-hole boiling flask of condensing reflux and nitrogen protection device, g MEK MEK, 1.0g dibutyl tin laurate, nitrogen protection, be heated to 60 DEG C and drip 376.4g XDI XDI, time for adding 30 minutes, react and drip 130.1g 2-hydroxyethyl methacry-late after 2 hours, time for adding is 30 minutes, react 2 hours again, add 201.1g MEK, react 48 hours under ice-water bath, until disappeared by peak, infrared spectrum detection of active isocyanate group 2275 place, obtain the MEK solution that solid content is the compound b3 of 80%.
B compou nd synthesis example b4:
Temperature control heating is with at 2000ml, mechanical raking, 298.0g pentaerythritol triacrylate PETA is added in the four-hole boiling flask of condensing reflux and nitrogen protection device, g MEK MEK, 1.0g dibutyl tin laurate, nitrogen protection, be heated to the 420.0g naphthalene-1 that 60 DEG C drip melting, 5-diisocyanate NDI, time for adding 30 minutes, react and drip 130.1g 2-hydroxyethyl methacry-late after 2 hours, time for adding is 30 minutes, react 2 hours again, add 212.0g MEK, react 48 hours under ice-water bath, until disappeared by peak, infrared spectrum detection of active isocyanate group 2275 place, obtain the MEK solution that solid content is the compound b4 of 80%.
B compou nd synthesis example b5:
Temperature control heating is with at 2000ml, mechanical raking, 298.0g pentaerythritol triacrylate PETA is added in the four-hole boiling flask of condensing reflux and nitrogen protection device, g MEK MEK, 1.0g dibutyl tin laurate, nitrogen protection, be heated to 60 DEG C and drip 524.0g dicyclohexyl methyl hydride diisocyanate HMDI, time for adding 30 minutes, react and drip 130.1g 2-hydroxyethyl methacry-late after 2 hours, time for adding is 30 minutes, react 2 hours again, add 238.0g MEK, react 48 hours under ice-water bath, until disappeared by peak, infrared spectrum detection of active isocyanate group 2275 place, obtain the MEK solution that solid content is the compound b5 of 80%.
Photosensitive composition of the present invention is dissolved in suitable solvent and is made into coating fluid.The following photosensitive liquid of extrusion coated on above-mentioned aluminum substrate, then at 110 DEG C dry 60 seconds, obtains 1.8g/m
2dry coating weight.
Above-mentioned thermoplasticity is used to receive submicron emulsion particle P01-P10; B: two urea ketone performed polymers synthesis example b1-b5 compounds, polyfunctional monomer, thermal polymerization, infrared absorbing agents and promoter make that embodiment is exempted from chemical treatment temperature-sensitive sensitive lithographic plate 1-10, used above-mentioned Comparative examples A 1-A5, K1-K5 receives submicron emulsion particle comparison example and exempts from chemical treatment temperature-sensitive sensitive lithographic plate 1-10.
Be below exemplifying embodiment of the present invention, but be not limited to following instance:
Embodiment 1
The protective seam 3 that the temperature-sensitive version that negative graph photosensitive composition is made comprises base version 1, is arranged on the negative graph photosensitive composition coating layer 2 in base version and is arranged on negative graph photosensitive composition coating layer.
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, use sine wave alternating current with 50A/dm
2current density electrolysis alligatoring 16 seconds.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 15A/dm
2current density, anodic oxidation 20 seconds.Washing.Sealing pores is carried out 18 seconds by the sodium silicate aqueous solution of 5% at 80 DEG C.Washing.Dry.The aluminum substrate support obtained like this, center line average boldness is 0.5um, the heavy 3.0g/dm of oxide film
2.
Photographic layer is coated with: at above-mentioned photosensitive liquid in the base version of hydrophilicity-imparting treatment below extrusion coated, then at 100 DEG C dry 60 seconds.Obtain 10mg/dm
2dry coating weight.Photosensitive liquid uses component (each component is by weight) below:
Protective seam is coated with: the protective seam solution that extrusion coated is following on photographic layer obtained above, then at 110 DEG C dry 60 seconds.Obtain 10mg/dm
2dry coating weight (each component by weight).
Protective seam formula (each component by weight)
PVAC polyvinylalcohol-205(Kuraray) 17
Polyvinylpyrrolidone PVPK30(Germany BASF) 3
Emulsifier op-10 (German Durham) 0.45
Deionized water 480
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
Base version, photographic layer and protective seam 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
Base version, photographic layer and protective seam 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, photographic layer and protective seam 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, photographic layer and protective seam 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, photographic layer and protective seam 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, photographic layer and protective seam 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, photographic layer and protective seam 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, photographic layer and protective seam 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, photographic layer and protective seam 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, photographic layer and protective seam 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 12
Version base, photographic layer and protective seam 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 13
Version base, photographic layer and protective seam is prepared by the method that embodiment 1 is identical.The dry coating of photographic 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 14
Version base, photographic layer and protective seam is prepared by the method that embodiment 1 is identical.The dry coat weight of photographic layer is just made to be 15mg/dm
2
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 15
Version base, photographic layer and protective seam is prepared by the method that embodiment 1 is identical.The dry coat weight of protective seam 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 16
Version base, photographic layer and protective seam is prepared by the method that embodiment 1 is identical.The dry coat weight of protective seam 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.
Comparative example 1-5
Version base, photographic layer and protective seam 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, photographic layer and protective seam 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, measure space of a whole page density with Ai Seli 528, measure its site performance with site instrument simultaneously; Machine on above-mentioned plate sample is normally printed (Heidelberg four look four drives high speed rotary press), investigates it and cross millboard number, pressrun.Plate performance sees attached list 2.
Shown by the detection application result of subordinate list, compare with radical polymerization mechanism plate with single hot melt, temperature-sensitive version plate of the present invention has multiple temperature-sensitive imaging mechanism, micron particles hot melt thermoplastic, the linear thermal polymerization of free radical and polyurethane mesh heat cross-linking can realized receiving, multiple temperature-sensitive imaging mechanism makes plate have, and light sensitivity is high, site is Well-recovered, the advantage of high pressrun, can directly be printed on the machine without any need for washing processing step after with infrared laser scanning imagery, very high pressrun can be obtained, realize environmental protection printing.
Subordinate list 1: emulsion particle performance table
Subordinate list 2: plate application performance table
Claims (18)
1. a negative graph photosensitive composition, it is characterized in that: it comprises receives micron particles two urea ketone performed polymer, polyfunctional monomer, thermal polymerization, infrared absorbing agents and promoter, by weight percentage, discrete micron particles of receiving accounts for the 30-70% of composition solid total amount, two urea ketone performed polymers account for the 10-50% of composition solid total amount, polyfunctional monomer accounts for the 10-30% of composition solid total amount, thermal polymerization accounts for the 1-20% of composition solid total amount, infrared absorbing agents accounts for the 1-20% of composition solid total amount, organic metal promoter accounts for the 0.5-5% of composition solid total amount.
2. negative graph photosensitive composition according to claim 1, it is characterized in that: it comprises type and receives micron particles, two urea ketone performed polymers, polyfunctional monomer, thermal polymerization and infrared absorbing agents, by weight percentage, micron particles of receiving accounts for the 40-60% of composition solid total amount, two urea ketone performed polymers account for the 20-40% of composition solid total amount, polyfunctional monomer accounts for the 10-20% of composition solid total amount, thermal polymerization accounts for the 5-15% of composition solid total amount, infrared absorbing agents accounts for the 5-15% of composition solid total amount, promoter accounts for the 1-3% of composition solid total amount.
3. negative graph photosensitive composition according to claim 1 and 2, is characterized in that: micron particles particle diameter received by described type is 50-300nm, and weight-average molecular weight is 40000-10000, has following structure:
R1, R2, R4 are H atom or methyl, and R3 is CH2CH2OH or CH2CH2CH2OH, R5 be COO (CH2CH2O) nH or COOCH2CH2NHCOO (CH2CH2O) nH, n is the integer of 20-60;
A, b, c, d are the percent by weight of corresponding copolymerization units, and a proportion is 40-70%, b proportion be 10-30%, c proportion be 10-30%, d proportion is 10-30%.
4. negative graph photosensitive composition according to claim 1 and 2, is characterized in that: described two urea ketone performed polymers are formed by unsaturated double-bond monomer and diisocyanate two urea ketonize;
Wherein unsaturated double-bond monomer is formed by connecting by the unsaturated double-bond monomer of hydroxyl and isocyanate group;
The unsaturated double-bond monomer of hydroxyl is any one in acrylic acid-2-hydroxyl ethyl ester, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacry-late, Hydroxypropyl methacrylate, pentaerythritol triacrylate;
Described isocyanates is diisocyanate, and diisocyanate comprises any one in aromatic diisocyanate, toluene diisocyanate, methyl diphenylene diisocyanate, PPDI, naphthalene diisocyanate or dimethyl diphenyl diisocyanate; Or isocyanates is 1,6-hexamethylene diisocyanate, 1-isocyanates-3-isocyanates, methylene-3,5,5-Trimethyl-cyclohexyl (isoflurane chalcone diisocyanate), 4, any one in the diisocyanate of 4'-hexylmethane, XDI, cyclohexane diisocyanate, tetramethylxylylene diisocyanate, 1,3-bis-(isocyanatomethyl) cyclohexane or cyclohexyl;
Wherein two urea ketone are by the dimer of two isocyanate group, and these two isocyanate group are two kinds of different structure isocyanates-R1-NCO or-R2-NCO, or the mutually isostructural isocyanates of one-RNCO.
5. negative graph photosensitive composition according to claim 1 and 2, is characterized in that: described two urea ketone performed polymers have following structure:
Wherein, R is:
,
,
,
,
。
6. negative graph photosensitive composition according to claim 1 and 2, it is characterized in that: described polyfunctional monomer is selected from polyfunctional group acrylic monomer, described acrylic monomer is diacrylate, 1,6-hexanediyl ester, pentaerythritol triacrylate and tetraacrylate, 1, any one in 3,5 one three one (2 one acrylyl oxy-ethyl) isocyanuric acid ester, hydroxypropyl glycerine base triacrylate, hydroxyethyl trimethylolpropane triacrylate, polyethylene glycol dimethacrylate.
7. negative graph photosensitive composition according to claim 1 and 2, is characterized in that: described thermal polymerization is any one in superoxide, azo compound, halogen substiuted compound in triazine class or salt.
8. photosensitive composition according to claim 7, is characterized in that: described superoxide is any one in hydrogen peroxide, ammonium persulfate, potassium persulfate, benzoyl peroxide, the benzoyl peroxide tert-butyl ester, methyl ethyl ketone peroxide; Described azo compound is any one in azoisobutyronitrile, ABVN, azo-bis-iso-dimethyl, band carboxyl, sulfonic azo-compound, azo diisobutyl amidine hydrochloride, described salt is salt compounded of iodine or sulfosalt, and it is that chlorine replaces compound in triazine class or bromine replaces compound in triazine class that each element of described halogen replaces compound in triazine class.
9. negative graph photosensitive composition according to claim 1 and 2, is characterized in that: the heat decomposition temperature of described thermal polymerization is at 150-200 DEG C.
10. negative graph photosensitive composition according to claim 1 and 2, it is characterized in that: described infrared absorbing agents is any one in 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, and the maximum absorption wavelength scope of this infrared absorbing agents is 750-1100 nm.
11. negative graph photosensitive compositions according to claim 1 and 2, is characterized in that: described infrared absorbing agents is cyanine dyes, the maximum absorption wavelength scope of this infrared absorbing agents is 750-850nm.
12. negative graph photosensitive compositions according to claim 1 and 2, it is characterized in that: described promoter is aminated compounds and organometallics, wherein aminated compounds is any one in triethylenediamine (TEDA), dimethyl cyclohexyl amine (DMCHA), dimethylethanolamine (DMEA), tetramethyl butane diamine (TMBDA), dimethylamino sulfuric ether (A-99) or benzyl dimethylamine; Organometallics is any one in the organometallics of mercury, lead, tin, bismuth, zinc, iron.
13. negative graph photosensitive compositions according to claim 12, is characterized in that: described tin organic compound is lauric acid diisobutyl tin or stannous octoate.
14. 1 kinds of temperature-sensitive versions made with the negative graph photosensitive composition described in claim 1 or 2; it is characterized in that, it comprises: substrate (1), the protective seam (3) being arranged on the negative graph photosensitive composition coating layer (2) on substrate and being arranged on negative graph photosensitive composition coating layer.
The temperature-sensitive version that 15. negative graph photosensitive compositions according to claim 14 are made, is characterized in that: aluminum substrate support is through electrolyzing and coarsening and anodic oxidation and carries out the aluminum substrate of sealing pores, and its center line average boldness is at 0.4-0.6 μm.
The temperature-sensitive version that 16. negative graph photosensitive compositions according to claim 14 are made, is characterized in that: above-mentioned negative graph photosensitive composition coating layer dry weight is 8-15mg/dm2.
The temperature-sensitive version that 17. negative graph photosensitive compositions according to claim 14 are made, is characterized in that: described protective seam dry weight is 5-20mg/dm2.
The temperature-sensitive version that 18. negative graph photosensitive compositions according to claim 14 are made; it is characterized in that: the material of described protective seam is water-soluble polymers, described water-soluble polymers is any one in polyvinyl alcohol (PVA), polyvinylpyrrolidone, acid cellulose derivant, gelatin or gum arabic and polypropylene phenol.
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