CN103879168B - A kind of long print journey temperature-sensitive version - Google Patents
A kind of long print journey temperature-sensitive version Download PDFInfo
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- CN103879168B CN103879168B CN201210560864.XA CN201210560864A CN103879168B CN 103879168 B CN103879168 B CN 103879168B CN 201210560864 A CN201210560864 A CN 201210560864A CN 103879168 B CN103879168 B CN 103879168B
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Abstract
The invention discloses a kind of long print journey temperature-sensitive version, it comprises support and thermal polymerization layer, and wherein thermal polymerization layer mainly contains: the molten unsaturated functional polymer adhesive of branched hydroxy group alkali, two urea ketone performed polymers, thermal polymerization, infrared absorbing agents, organic metal promoter, the main chain of the molten unsaturated functional polymer adhesive of described branched hydroxy group alkali is at least containing 3 functional unit :-A-B-C-, wherein A: unsaturated functional unit: be carboxyl open loop substituent methyl glycidyl acrylate or 3, 4-epoxycyclohexyl-methyl acrylate, B: branched hydroxy group functional unit: be 2-hydroxyethyl methacry-late or acrylic acid-2-hydroxyl ethyl ester, C: the molten functional unit of alkali: be methacrylic acid or acrylic acid, plate of the present invention has free radical thermal polymerization and the dual thermographic ability of polyurethane heat cross-linking, polyurethane mesh heat cross-linking is realized while realizing free radical linear polymerization, strong polarity ammonia ester bond has very high wearability, ammonia ester bond cross-linked network makes plate can obtain the pressrun of superelevation.
Description
Technical field
The invention belongs to printing technology, be specifically related to a kind of long print journey temperature-sensitive version and preparation method thereof.
Background technology
Lithography technique moves towards CTP technology (being called for short CTP technology) from traditional laser photo film copy PS platemaking technology comprehensively, and CTP plate is also popularized gradually.CTP plate kind is a lot, and relatively more universal comprises Silver Salt Diffusion Transfer CTP Plate material, UV-CTP version, purple laser polymerization CTP plate, thermal CTP plate material etc.Wherein most popular is thermal CTP plate material.At present, improve the performance of heat-sensitive CTP plate further, particularly increase the solvent resistance of plate, the resistance to print ability improving plate is the focus of thermal CTP plate material exploitation.
Improve the resistance to print ability of 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.In general, the good plate of solvent resistance has higher wearability, 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 organic matter 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 copolymer, styrene maleic anhydride copolymer, phenolic resins, maleated wood rosin and their composition, have solvent resistant effect, the maleimide of especially N-replacement, methyl acrylamide, polyvinyl acetaldehyde polymer can improve the print journey of forme; Kodak patent CN101321632A is disclosed introduces phosphoric acid or adamantane side base at polymer, 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 wearability of plate coating, improves plate pressrun; Kodak is at WO2004/033206, a kind of QHB phenol-formaldehyde resin modified is disclosed in CN200380104739.7, with iso-cytosine (2-amino-4-hydroxy pyrimidine) and isocyanate-modified phenolic resins, form strong polarity tetrahydrochysene bonding structure, be used in multilayer heat-sensitive version upper strata i.e. the second polymer layer, to improve the wearability 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 derivative thereof; Agfa Corp. EP [31] 02102446.8, CN1688441A discloses a kind of method of modifying by phenolic hydroxyl group distant pawl group, phenolic resins being carried out to diazol 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 organic matter.
We know, macromolecule resin is divided into linear structure and network structure, 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 wearability.
Temperature-sensitive version production process is generally that heat-sensitive composition is coated on supporter as on aluminum substrate by the mode of dip-coating, spraying or extrusion coated as a solution, so be difficult to realize adding the reticular polymer resin being difficult to dissolve in heat-sensitive composition to obtain good wearability to improve plate pressrun.
For the problems referred to above, the present invention devises a kind of Thermal sensitive plate composition, and it comprises support and thermal polymerization layer, and wherein thermal polymerization layer mainly contains: the molten unsaturated functional polymer adhesive of a branched hydroxy group alkali; B bis-urea ketone performed polymer; C thermal polymerization; D infrared absorbing agents; E organic metal promoter.Plate has brand-new dual thermographic mechanism, and can realize polyurethane mesh heat cross-linking while realizing the linear thermal polymerization of free radical, the ammonia ester bond of strong polarity has very high wearability, and ammonia ester bond cross-linked network makes plate can obtain the pressrun of superelevation.
Summary of the invention
The object of the invention is to the shortcoming solving temperature-sensitive version solvent resistant ability and the Nai Yin ability existed in existing temperature-sensitive platemaking technology, particularly be difficult to realize obtaining good wearability to improve the problem of plate pressrun by adding the reticular polymer resin being difficult to dissolve in heat-sensitive composition, the present invention devises a kind of temperature-sensitive version with dual thermographic mechanism completely newly, this temperature-sensitive version comprises support and thermal polymerization layer, and wherein thermal polymerization layer mainly contains: the molten unsaturated functional polymer adhesive of a branched hydroxy group alkali; B bis-urea ketone performed polymer; C thermal polymerization; D infrared absorbing agents; E organic metal promoter.Plate has free radical thermal polymerization and the dual thermographic ability of polyurethane heat cross-linking, polyurethane mesh heat cross-linking is realized while realizing free radical linear polymerization, strong polarity ammonia ester bond has very high wearability, and ammonia ester bond cross-linked network makes plate can obtain the pressrun of superelevation.
For achieving the above object, the present invention adopts following technical scheme:
The present invention devises a kind of temperature-sensitive version with dual thermographic mechanism completely newly, and it comprises support and thermal polymerization layer, and wherein thermal polymerization layer mainly contains: the molten unsaturated functional polymer adhesive of a branched hydroxy group alkali; B bis-urea ketone performed polymer; C thermal polymerization; D infrared absorbing agents; E organic metal promoter.First plate has the ability of free radical thermal polymerization, laser energy is passed to thermal polymerization by d 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 a molten unsaturated functional polymer adhesive of branched hydroxy group alkali and b bis-urea ketone performed polymer, realizes free radical linear polymerization, simultaneously, the heat of infrared laser makes two urea ketone in b bis-urea ketone performed polymer produce thermofission by the laser energy that d infrared absorbing agents transmits, produce active isocyanate base (-NCO), there is polyurethane reaction in the branched hydroxy group (-OH) of active isocyanate base (-NCO) under the catalytic action of e organic metal promoter and in the molten unsaturated functional polymer adhesive of a branched hydroxy group alkali, 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 wearability, ammonia ester bond cross-linked network makes plate can obtain the pressrun of superelevation, plate relies on the molten group carboxyl (-COOH) of alkali in the molten unsaturated functional polymer adhesive of a branched hydroxy group alkali to realize alkali development.
Below the present invention is elaborated:
The present invention devises a kind of Thermal sensitive plate composition, and it comprises support and thermal polymerization layer, and wherein thermal polymerization layer mainly contains: the molten unsaturated functional polymer adhesive of a branched hydroxy group alkali; B bis-urea ketone performed polymer; C thermal polymerization; D infrared absorbing agents; E organic metal promoter.Plate has free radical thermal polymerization and the dual thermographic ability of polyurethane heat cross-linking, polyurethane mesh heat cross-linking is realized while realizing free radical linear polymerization in energy, strong polarity ammonia ester bond has very high wearability, and ammonia ester bond cross-linked network makes plate can obtain the pressrun of superelevation.
First a in thermal polymerization layer is described: the molten unsaturated functional polymer adhesive of branched hydroxy group alkali.
Design a kind of Thermal sensitive plate, first it is considered that the thermal polymerization layer of plate, in thermal polymerization layer, need a kind of important matrix resin and film-forming resin, resin can after guarantee coating fluid drying film forming, thermal polymerization layer is attached on support.Film-forming resin can select phenolic resins, acrylic resin, polyurethane resin etc.The present invention selects acrylic compounds film-forming resin.
Film-forming resin, according to plate mechanism needs, is usually designed to the functional resin of the band functional group that can participate in plate mechanism.The film-forming resin of the present invention's design is also functional film-forming resin, i.e. a: the molten unsaturated functional polymer adhesive of branched hydroxy group alkali.It is a kind of macromolecule filming adhesive, and simultaneously according to plate needs, polymer binder main chain contains specific function group, and polymer binder main chain is at least containing 3 functional unit :-A-B-C-
A: unsaturated functional unit: be carboxyl open loop substituent methyl glycidyl acrylate (GMA) or 3,4-epoxycyclohexyl-methyl acrylate (CMA)
B: branched hydroxy group functional unit: be 2-hydroxyethyl methacry-late (HEMA) or acrylic acid-2-hydroxyl ethyl ester (HEA).
C: the molten functional unit of alkali: be methacrylic acid (MAA) or acrylic acid (MA).
Specifically describe above-mentioned 3 functional units below:
A: unsaturated functional unit:
The Thermal sensitive plate composition of the present invention's design has the function of free radical thermal polymerization, realize free radical thermal polymerization, unsaturated double-bond must be contained in plate composition, devise 2 components in temperature-sensitive version composition of the present invention and contain unsaturated double-bond, be i.e. the molten unsaturated functional polymer adhesive of a branched hydroxy group alkali and b bis-urea ketone performed polymer.The present invention devises A in the molten unsaturated functional polymer adhesive of a branched hydroxy group alkali: unsaturated functional unit.
Unsaturated double-bond to be formed in macromolecule resin side chain, method has a lot, and the method that can realize has and replaces Graft Method, branched hydroxy group and NCO reactive grafting method, carboxyl and hydroxy esterification Graft Method, carboxyl and epoxy ring-opening reactive grafting method etc. by side chain halogen radical.The present invention forms unsaturated double-bond and selects carboxyl and epoxy ring-opening reactive grafting method in macromolecule resin side chain.Can have a lot with the double bond containing epoxide of carboxyl generation ring-opening polymerisation, as GMA, 3,4-epoxycyclohexyl-methyl acrylate, 3,4-epoxycyclohexyl-methyl methacrylates, 3,4-epoxycyclohexyl isopropyl methacrylate etc.The present invention is preferred:
GMA (GMA):
Or 3,4-epoxycyclohexyl-methyl acrylate (CMA):
First the matrix resin of synthesis containing carboxyl branches, then by carboxyl open loop substituent methyl glycidyl acrylate (GMA) or 3,4-epoxycyclohexyl-methyl acrylate (CMA), forms side chain unsaturated double-bond.
B: branched hydroxy group functional unit:
The Thermal sensitive plate composition of the present invention's design has the function of heat cross-linking, the heat of infrared laser makes two urea ketone in b bis-urea ketone performed polymer produce thermofission by the laser energy that d infrared absorbing agents transmits, produce active isocyanate base (-NCO), there is polyurethane reaction in the branched hydroxy group (-OH) of active isocyanate base (-NCO) under the catalytic action of e organic metal promoter and in the molten unsaturated functional polymer adhesive of a branched hydroxy group alkali, form ammonia ester bond (-NHCOO), while realizing free radical linear polymerization, realize polyurethane mesh heat cross-linking.
Branched hydroxy group to be introduced in macromolecule resin chain, the acrylic monomer of hydroxyl can be selected as copolymerization units, the acrylic monomer of hydroxyl has acrylic acid-2-hydroxyl ethyl ester, 2-hydroxypropyl acrylate (HPA), 2-hydroxyethyl methacry-late (HEMA), Hydroxypropyl methacrylate (HPMA) etc., and the acrylic monomer of the particularly preferred hydroxyl of the present invention is the carboxyl in methacrylic acid (MAA) or acrylic acid (MA).
C: the molten functional unit of alkali:
The Thermal sensitive plate composition of the present invention's design has the function of alkali development.Plate heat-sensitive layer is under the effect of infrared laser, areas issues raw radical polymerization and polyurethane heat cross-linking at infrared laser thermal energy, areas heat-sensitive layer molecular weight sharply becomes large, and non-sensible heat part heat-sensitive layer molecular weight is constant, under alkaline-based developer effect, because sensible heat part and non-sensible heat part heat susceptible coating exist the difference of molecular weight, the two acidic-group and alkali generation acid-base neutralization reaction rate there are differences, so coating rate of dissolution in alkaline developer is different, non-sensible heat part is due to molecular weight, first coating dissolves, expose hydrophilic aluminum substrate, and the coating of sensible heat part becomes very large due to generation radical polymerization and polyurethane heat cross-linking molecular weight, only have a small amount of coating dissolution, aluminum substrate can not be exposed, so sensible heat coating oleophylic is black, realize printing.
The acidic-group of energy and alkaline-based developer generation neutralization reaction has all energy such as carboxyl, sulfonic group, phosphate, phenolic hydroxyl group dissociation to go out the lewis acid of proton hydrogen.The molten group of alkali of the present invention selects carboxyl.Carboxyl to be introduced in macromolecule resin chain, carboxylic acrylic monomer can be selected as copolymerization units, carboxylic acrylic monomer acrylic or methacrylic acid having acrylic acid, methacrylic acid, halogen substiuted etc., the particularly preferred carboxylic acrylic monomer of the present invention is methacrylic acid (MAA) or acrylic acid (MA).
A in thermal polymerization layer of the present invention: the unsaturated group contained by the molten unsaturated functional polymer adhesive of branched hydroxy group alkali is carbon-carbon double bond, and contained carbon-carbon double bond amount can control by iodine number.Assay method: first prepare Wei Yisi reagent (Wijsreagent, lodine chloride is dissolved in concentration 0.2mol/1L in acetic acid) 25ml, the quantity of resin sample depends on degree of unsaturation, make Wei Yisi reagent have 100% ~ 150% excessive.Sample is dissolved in 20ml MEK, then adds mentioned reagent, keep temperature 20 ~ 25 DEG C, 30min; Add 20ml liquor kalii iodide [15% (quality)] and 100ml water, with the titration of 0.1mol/L sodium thiosulfate, with starch solution (10%) for indicator.The molten unsaturated functional polymer adhesive iodine number scope control of branched hydroxy group alkali of the present invention is at 20-100g iodine/100g resin.
A in thermal polymerization layer of the present invention: the branched hydroxy group content contained by the molten unsaturated functional polymer adhesive of branched hydroxy group alkali can control by hydroxyl value, bioassay standard is adopted international standards ISO2554-1974 " mensuration of plastics---unsaturated polyester resin---hydroxyl value ".The molten unsaturated functional polymer adhesive hydroxyl value scope control of branched hydroxy group alkali of the present invention is at 100-180mgKOH/g resin.
A in thermal polymerization layer of the present invention: the molten group of alkali contained by the molten unsaturated functional polymer adhesive of branched hydroxy group alkali is carboxyl, contained carboxyl amount can control with acid number, and the mensuration of acid number is undertaken by GB2895-82 " mensuration of unsaturated polyester resin acid number ".The molten unsaturated functional polymer adhesive acid value of branched hydroxy group alkali of the present invention controls at 20-120mgKOH/g resin.
A in thermal polymerization layer of the present invention: the molten unsaturated functional polymer binder wt mean molecule quantity of branched hydroxy group alkali can utilize gel permeation chromatography to measure.A: the molten unsaturated functional polymer binder wt mean molecule quantity of branched hydroxy group alkali controls in 20,000-10 ten thousand (polystyrene standard).
Synthetic method can select solution polymerization process, emulsion polymerization, interfacial polymerization etc., and the copolymer of synthesis can have rule, also can be random.In building-up process, operable solvent comprises water, methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, butanols, acetone, MEK, cyclohexanone, ethyl acetate, butyl acetate, oxolane, 1, 4-dioxane, N, dinethylformamide, dimethylacetylamide acetone, methyl ethyl ketone, cyclohexane, ethylene dichloride, toluene, EGME, ethylene glycol ethyl ether, glycol dimethyl ether, propylene glycol monomethyl ether, propylene-glycol ethyl ether, acetylacetone,2,4-pentanedione, DAA, ethylene glycol monomethyl ether acetate, ethyl cellosolve acetate, glycol isopropyl ether, butyl glycol ether acetic acid esters, 3-methoxypropanol, methoxymethoxy ethanol, diethylene glycol dimethyl ether, diethylene glycol ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol methyl ether acetate, propylene-glycol ethyl ether acetic acid esters, methyl-sulfoxide, methyl lactate and ethyl lactate etc., or their mixture.
Secondly b: two urea ketone performed polymers in thermal polymerization layer are described.
The Thermal sensitive plate composition of the present invention's design has the function of heat cross-linking, the heat of infrared laser makes two urea ketone in b bis-urea ketone performed polymer produce thermofission by the laser energy that d infrared absorbing agents transmits, produce active isocyanate base (-NCO), there is polyurethane reaction in the branched hydroxy group (-OH) of active isocyanate base (-NCO) under the catalytic action of e organic metal promoter and in the molten unsaturated functional polymer adhesive of a branched hydroxy group alkali, form ammonia ester bond (-NHCOO), while realizing free radical linear polymerization, realize polyurethane mesh heat cross-linking.
Components b two urea ketone performed polymer in Thermal sensitive plate composition of the present invention, has following general structure:
Wherein, R is:
，
，
，
，
。
Laser pyrolysis mechanism schematic diagram is as follows:
Two urea ketone are by the dimer of two NCOs, and these two NCOs 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 NCOs 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 symmetrical configuration providing NCO 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 NCO by hydroxyl, so the isocyanates selected by the present invention is vulcabond.Vulcabond comprises aromatic diisocyanates toluene di-isocyanate(TDI) (TDI) and methyl diphenylene diisocyanate (MDI), PPDI (PPDI), naphthalene diisocyanate (NDI), dimethyl diphenyl vulcabond (TODI); Fatty and alicyclic isomers 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 vulcabond that b bis-urea ketone performed polymer in synthesis the present invention is selected is aromatic diisocyanate or the vulcabond containing cyclohexyl.Consider that the ordinary temperature stability of two urea ketone performed polymers is good, laser pyrolysis, the vulcabond that the present invention selects is methyl diphenylene diisocyanate (MDI), 4,4'-hexylmethane (H12MDI), XDI (XDI), toluene di-isocyanate(TDI) (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 NCO by hydroxyl, hydroxyl
Unsaturated double-bond monomer have 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).
Amount of component b in temperature-sensitive version 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 c by d infrared absorbing agents by the heat of infrared laser: thermal polymerization, c: thermal polymerization discharges competent primary free radical, primary group of free radicals causes the unsaturated double-bond in a molten unsaturated functional polymer adhesive of branched hydroxy group alkali and b bis-urea ketone performed polymer, realizes free radical linear polymerization.
Thermal polymerization decomposes in the present invention generates primary group of free radicals, causes unsaturated double-bond generation radical polymerization.The thermal polymerization kind that can cause radical polymerization has a lot, comprises peroxide as hydrogen peroxide, ammonium persulfate, potassium peroxydisulfate, benzoyl peroxide, the benzoyl peroxide tert-butyl ester, methyl ethyl ketone peroxide etc.; Azo compound is as azodiisobutyronitrile, 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.
Component d in temperature-sensitive version composition of the present invention is described in detail in detail: infrared absorbing agents below.
Component d in temperature-sensitive version composition of the present invention: infrared absorbing agents mainly plays energy trasfer, laser energy is passed to thermal polymerization by d 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 a molten unsaturated functional polymer adhesive of branched hydroxy group alkali and b bis-urea ketone performed polymer, realizes free radical linear polymerization; Simultaneously, the heat of infrared laser makes two urea ketone in b bis-urea ketone performed polymer produce thermofission by the laser energy that d infrared absorbing agents transmits, produce active isocyanate base (-NCO), there is polyurethane reaction in the branched hydroxy group (-OH) of active isocyanate base (-NCO) under the catalytic action of e organic metal promoter and in the molten unsaturated functional polymer adhesive of a branched hydroxy group alkali, form ammonia ester bond (-NHCOO), while realizing free radical linear polymerization, realize polyurethane mesh heat cross-linking.
The maximum absorption wavelength scope of infrared absorbing compounds contained by heat susceptible coating is 780-1100nm, is selected from carbon black, triarylamine dyes, thiazole dye, indoline dye, oxazole dyestuff, cyanine dyes, polyaniline dye, polypyrole dye, polythiophene dye, methine dyes, naphthoquinone dyestuff, leuco dye and phthalocyanine color and dyestuff etc.Component d in temperature-sensitive version composition of the present invention: the cyanine dyes of infrared absorbing agents to be absorption maximum scope be 760-1200nm.
Component e in temperature-sensitive version 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 b bis-urea ketone performed polymer produce thermofission by the laser energy that d infrared absorbing agents transmits, produce active isocyanate base (-NCO), active isocyanate base (-NCO) is at e: polyurethane reaction occurs the branched hydroxy group (-OH) under the catalytic action of organic metal promoter and in the molten unsaturated functional polymer adhesive of a branched hydroxy group alkali, form ammonia ester bond (-NHCOO), while realizing free radical linear polymerization, realize polyurethane mesh heat cross-linking.
Polyurethane reaction generally needs catalyst, can promote that the catalyst of polyurethane reaction has a lot, and Polyurethane catalyst can be divided into two large class, amines and organo-metallic compounds.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.; Organo-metallic compound is as organo-metallic compound of mercury, lead, tin, bismuth, zinc, iron etc.Component e in temperature-sensitive version composition of the present invention: organic metal promoter selects stable, efficient organic metal tin compound, as laurate diisobutyl tin, stannous octoate etc.
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 electrolyte used can be acid, alkali or the aqueous solution of salt or the aqueous solution containing organic solvent.Wherein, electrolyte is made with the aqueous solution of hydrochloric acid, nitric acid or their salt better.First aluminium plate is placed in the aqueous solution of NaOH, potassium hydroxide, sodium carbonate, sodium metasilicate etc. of 1%-30%, at the temperature of 20-80 DEG C, carries out the chemical attack of 5-250 second.Then in the nitric acid or sulfuric acid of 10%-30% with the temperature of 20-70 DEG C in and, to remove grey matter.Like this through the aluminium plate of cleaning, at the temperature of 10-6O DEG C, with square wave, the bench-type ripple or sine wave etc. of positive and negative sexual intercourse change, with the current density of 5-100A/d ㎡, electrolytic treatments 10-300 second in the electrolyte of nitric acid or hydrochloric acid.Then, the aluminium plate through electrolysis carries out anodized.Anodic oxidation uses sulfuric acid process usually.The concentration of the sulfuric acid used is 5-30%, and current density is 1-15A/d ㎡, and oxidizing temperature is at 20-60 DEG C, and oxidization time is 5-250 second, to form the oxide-film of 1-10g/ ㎡.The oxide-film of such formation has higher oxide-film micropore usually, and adsorption capacity is comparatively strong, is easy to adhere to foul.So usually also need to carry out sealing pores.Sealing pores can use various method, is good to reach the 50-80% volume of closed oxide-film micropore.Last on the aluminium sheet through above-mentioned process, coating PVPA, thickness is 3mg/ ㎡.
Some other auxiliary agents can also be comprised, as institute's solvent, normal temperature thermal polymerization inhibitor, coating colours, surfactant etc. in heat susceptible coating.
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, oxolane, toluene, EGME, ethylene glycol ethyl ether, glycol dimethyl ether, propylene glycol monomethyl ether, propylene-glycol ethyl ether, acetylacetone,2,4-pentanedione, cyclohexanone, DAA, ethylene glycol monomethyl ether acetate, ethyl cellosolve acetate, glycol isopropyl ether, butyl glycol ether acetic acid esters, 3-methoxypropanol, methoxymethoxy ethanol, diethylene glycol dimethyl ether, diethylene glycol ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol methyl ether acetate, propylene-glycol ethyl ether acetic acid esters, N.N-dimethyl formamide, methyl-sulfoxide, methyl lactate and ethyl lactate etc.Solvent can use with pure material form or form of mixtures.
The solid content of coating mixture is generally 2-50% (weight), and in the present invention, the molten unsaturated functional polymer adhesive of a branched hydroxy group alkali and b bis-urea ketone performed polymer combinationally use, a component accounts for a, the 60-80% of b gross weight, b component accounts for a, the 20-40% of b gross weight.
Normal temperature thermal polymerization inhibitor is to prevent sheet material to be polymerized at normal temperatures, improves the ordinary temperature stability of plate.Thermal polymerization inhibitor comprises: quinhydrones, NO free radical piperidine alcohols, p methoxy phenol, BHT, 1,2,3,-thrihydroxy-benzene, tert-butyl catechol, benzoquinones, 4,4'-thiobis-(3 methy 6 tert butyl phenol), 2,2 '-di-2-ethylhexylphosphine oxide (4-methyl isophthalic acid 6-tert-butyl phenol), and uncle's cerium salt of N-nitroso phenylhydroxylamine etc.
Heat susceptible coating contains layer colouring agent.In order to increase the image density after the plate-making of temperature-sensitive version, being convenient to carry out visual inspection or graphical analysis measurement device measurement plate performance to temperature-sensitive version after plate-making, in the temperature-sensitive layer of temperature-sensitive version of the present invention, adding layer colouring agent.It comprises: crystal violet, ethyl violet, crystal violet, purple in crystallization, Victoria blue, glossy dark green, oil blue, oil yellow, rhodamine B, crystal violet rowland, malachite green, methylene blue, triazines etc.
Heat susceptible coating contains surfactant, can select non-ionic surface active agent, amphoteric surfactant, silicon-containing surfactant, fluorine-containing surfactant etc.As betaines, tristerin class, sorbic acid palm fibre grease class, polysiloxane-based, poly-fluoroalkyl ethers.
As temperature-sensitive version of the present invention, optionally can be coated with layer protective layer on heat susceptible coating, prevent 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 polymer of preferred tool, as poly-(vinyl alcohol), polyvinylpyrrolidone, acid cellulose derivative, gelatin, gum arabic and poly-(allyl phenol etc.These materials can obtain as the main component of protective layer and refuse oxygen and development removeability very well.Take coating nitrogen replacement technique, plate vacuum-packed technique and vacuumize plate-making technology in producing at plate now; the shadow of pollutant to plate in oxygen or other environment can be wanted to drop to minimum; the plate of adding system of the present invention is insensitive to the pollutant in oxygen or air, so protective layer can choice for use or do not use.
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.
Detailed description of the invention
The molten unsaturated functional polymer adhesive of synthesis a branched hydroxy group alkali: synthesis example a1-a12
Raw material can obtain from following company: GMA GMA: Mitsubishi Chemical; 3,4-epoxycyclohexyl-methyl acrylate (CMA): Mitsubishi Chemical, CMA-20; Methacrylic acid MAA, acrylic acid MA: German Degussa; 2-hydroxyethyl methacry-late HEMA: Mitsubishi Li Yang Co., Ltd.; Benzyltrimethylammonium chloride TMBAC: be sure to win Chemical Co., Ltd. in Wuxi; NO free radical piperidine alcohols ZJ701 Nangong City Sheng Hua Chemical Co., Ltd.; Triphenylphosphine TPP: Shanghai Wei Fang Fine Chemical Co., Ltd; DMA DMAC: Mitsubishi Chemical; Azodiisobutyronitrile AIBN: Tianjin good fortune chemical reagent factory in morning.
A compou nd synthesis example a1:
Temperature control heating is with at 3000ml, mechanical agitation, 1250gDMAC (the N that 1500g crosses through anhydrous sodium sulfate drying is added in the four-hole boiling flask of condensing reflux and nitrogen protection device, N-dimethylacetylamide), nitrogen replaces 30 minutes, following mixture is dripped: 172.2g methacrylic acid MAA at 60 DEG C, 130.1g 2-hydroxyethyl methacry-late HEMA, 2g azodiisobutyronitrile AIBN, time for adding is 15 minutes, drip off rear reaction and within 5 hours, add 2gAIBN (azodiisobutyronitrile), react 5 hours again, then 12g benzyltrimethylammonium chloride TMBAC is added, 6g triphenylphosphine TPP, 6g NO free radical piperidine alcohols (ZJ701), 184.8g GMA GMA, react 2 hours at being warming up to 90 DEG C, react at being warming up to 110 DEG C again and terminate for 2 hours, reactant is separated out in the 10 liters of deionized waters adding 10g glacial acetic acid, then deionized water is fully washed, 40 DEG C of vacuum drying, obtain the molten unsaturated functional polymer adhesive a1 of branched hydroxy group alkali.Weight average molecular weight Mw=95200, iodine number Iv=52.1g iodine/100g resin, hydroxyl value Hv=115.2mgKOH/g resin, acid number Av=80.0mgKOH/g resin.
A compou nd synthesis example a2:
Temperature control heating is with at 3000ml, mechanical agitation, 2300gDMAC (the N that 1500g crosses through anhydrous sodium sulfate drying is added in the four-hole boiling flask of condensing reflux and nitrogen protection device, N-dimethylacetylamide), nitrogen replaces 30 minutes, following mixture is dripped: 172.2g methacrylic acid MAA at 60 DEG C, 130.1g 2-hydroxyethyl methacry-late HEMA, 2g azodiisobutyronitrile AIBN, time for adding is 15 minutes, drip off rear reaction and within 5 hours, add 2gAIBN (azodiisobutyronitrile), react 5 hours again, then 13g benzyltrimethylammonium chloride TMBAC is added, 6.5g triphenylphosphine TPP, 6.5g NO free radical piperidine alcohols (ZJ701) 273.3g3, 4-epoxycyclohexyl-methyl acrylate CMA, react 2 hours at being warming up to 90 DEG C, react at being warming up to 110 DEG C again and terminate for 2 hours, reactant is separated out in the 10 liters of deionized waters adding 10g glacial acetic acid, then deionized water is fully washed, 40 DEG C of vacuum drying, obtain the molten unsaturated functional polymer adhesive a2 of branched hydroxy group alkali.Weight average molecular weight Mw=54300, iodine number Iv=66.1g iodine/100g resin, hydroxyl value Hv=97.5mgKOH/g resin, acid number Av=48.7mgKOH/g resin.
A compou nd synthesis example a3:
Temperature control heating is with at 5000ml, mechanical agitation, 4420gDMAC (the N that 1500g crosses through anhydrous sodium sulfate drying is added in the four-hole boiling flask of condensing reflux and nitrogen protection device, N-dimethylacetylamide), nitrogen replaces 30 minutes, following mixture is dripped: 129.2g methacrylic acid MAA at 60 DEG C, 174.2g acrylic acid-2-hydroxyl ethyl ester HEA, 2g azodiisobutyronitrile AIBN, time for adding is 15 minutes, drip off rear reaction and within 5 hours, add 2gAIBN (azodiisobutyronitrile), react 5 hours again, then 9.0g benzyltrimethylammonium chloride TMBAC is added, 4.5g triphenylphosphine TPP, 4.5g NO free radical piperidine alcohols (ZJ701), 187.6g GMA GMA, react 2 hours at being warming up to 90 DEG C, react at being warming up to 110 DEG C again and terminate for 2 hours, reactant is separated out in the 10 liters of deionized waters adding 10g glacial acetic acid, then deionized water is fully washed, 40 DEG C of vacuum drying, obtain the molten unsaturated functional polymer adhesive a3 of branched hydroxy group alkali.Weight average molecular weight Mw=20010, iodine number Iv=68.2g iodine/100g resin, hydroxyl value Hv=171.2mgKOH/g resin, acid number Av=20.5mgKOH/g resin.
A compou nd synthesis example a4:
Temperature control heating is with at 3000ml, mechanical agitation, 1210gDMAC (the N that 1500g crosses through anhydrous sodium sulfate drying is added in the four-hole boiling flask of condensing reflux and nitrogen protection device, N-dimethylacetylamide), nitrogen replaces 30 minutes, following mixture is dripped: 172.2g methacrylic acid MAA at 60 DEG C, 116.1g acrylic acid-2-hydroxyl ethyl ester HEA, 2g azodiisobutyronitrile AIBN, time for adding is 15 minutes, drip off rear reaction and within 5 hours, add 2gAIBN (azodiisobutyronitrile), react 5 hours again, then 9g benzyltrimethylammonium chloride TMBAC is added, 4.5g triphenylphosphine TPP, 4.5g NO free radical piperidine alcohols (ZJ701), 182.2g3, 4-epoxycyclohexyl-methyl acrylate CMA, react 2 hours at being warming up to 90 DEG C, react at being warming up to 110 DEG C again and terminate for 2 hours, reactant is separated out in the 10 liters of deionized waters adding 10g glacial acetic acid, then deionized water is fully washed, 40 DEG C of vacuum drying, obtain the molten unsaturated functional polymer adhesive a4 of branched hydroxy group alkali.Weight average molecular weight Mw=50500, iodine number Iv=53.9g iodine/100g resin, hydroxyl value Hv=119.6mgKOH/g resin, acid number Av=120.0mgKOH/g resin.
A compou nd synthesis example a5:
Temperature control heating is with at 3000ml, mechanical agitation, 1400gDMAC (the N that 1500g crosses through anhydrous sodium sulfate drying is added in the four-hole boiling flask of condensing reflux and nitrogen protection device, N-dimethylacetylamide), nitrogen replaces 30 minutes, following mixture is dripped: 144.2g acrylic acid MA at 60 DEG C, 130.1g 2-hydroxyethyl methacry-late HEMA, 2g azodiisobutyronitrile AIBN, time for adding is 15 minutes, drip off rear reaction and within 5 hours, add 2gAIBN (azodiisobutyronitrile), react 5 hours again, then 9.5g benzyltrimethylammonium chloride TMBAC is added, 4.8g triphenylphosphine TPP, 4.8g NO free radical piperidine alcohols (ZJ701), 191.5g GMA GMA, react 2 hours at being warming up to 90 DEG C, react at being warming up to 110 DEG C again and terminate for 2 hours, reactant is separated out in the 10 liters of deionized waters adding 10g glacial acetic acid, then deionized water is fully washed, 40 DEG C of vacuum drying, obtain the molten unsaturated functional polymer adhesive a5 of branched hydroxy group alkali.Weight average molecular weight Mw=70120, iodine number Iv=56.2g iodine/100g resin, hydroxyl value Hv=120.8mgKOH/g resin, acid number Av=118.5mgKOH/g resin.
A compou nd synthesis example a6:
Temperature control heating is with at 3000ml, mechanical agitation, 1550gDMAC (the N that 1500g crosses through anhydrous sodium sulfate drying is added in the four-hole boiling flask of condensing reflux and nitrogen protection device, N-dimethylacetylamide), nitrogen replaces 30 minutes, following mixture is dripped: 144.2g acrylic acid MA at 60 DEG C, 130.1g 2-hydroxyethyl methacry-late HEMA, 2g azodiisobutyronitrile AIBN, time for adding is 15 minutes, drip off rear reaction and within 5 hours, add 2gAIBN (azodiisobutyronitrile), react 5 hours again, then 13g benzyltrimethylammonium chloride TMBAC is added, 6.5g triphenylphosphine TPP, 6.5g NO free radical piperidine alcohols (ZJ701), 273.3g3, 4-epoxycyclohexyl-methyl acrylate CMA, react 2 hours at being warming up to 90 DEG C, react at being warming up to 110 DEG C again and terminate for 2 hours, reactant is separated out in the 10 liters of deionized waters adding 10g glacial acetic acid, then deionized water is fully washed, 40 DEG C of vacuum drying, obtain the molten unsaturated functional polymer adhesive a6 of branched hydroxy group alkali.Weight average molecular weight Mw=75080, iodine number Iv=70.0g iodine/100g resin, hydroxyl value Hv=102.5mgKOH/g resin, acid number Av=51.3mgKOH/g resin.
A compou nd synthesis example a7:
Temperature control heating is with at 3000ml, mechanical agitation, 1040gDMAC (the N that 1500g crosses through anhydrous sodium sulfate drying is added in the four-hole boiling flask of condensing reflux and nitrogen protection device, N-dimethylacetylamide), nitrogen replaces 30 minutes, following mixture is dripped: 144.2g acrylic acid MA at 60 DEG C, 174.2g acrylic acid-2-hydroxyl ethyl ester HEA, 2g azodiisobutyronitrile AIBN, time for adding is 15 minutes, drip off rear reaction and within 5 hours, add 2gAIBN (azodiisobutyronitrile), react 5 hours again, then 8.0g benzyltrimethylammonium chloride TMBAC is added, 4.08g triphenylphosphine TPP, 4.08g NO free radical piperidine alcohols (ZJ701), 170.6g GMA GMA, react 2 hours at being warming up to 90 DEG C, react at being warming up to 110 DEG C again and terminate for 2 hours, reactant is separated out in the 10 liters of deionized waters adding 10g glacial acetic acid, then deionized water is fully washed, 40 DEG C of vacuum drying, obtain the molten unsaturated functional polymer adhesive a7 of branched hydroxy group alkali.Weight average molecular weight Mw=100030, iodine number Iv=62.3g iodine/100g resin, hydroxyl value Hv=172.6mgKOH/g resin, acid number Av=34.4mgKOH/g resin.
A compou nd synthesis example a8:
Temperature control heating is with at 3000ml, mechanical agitation, 1790gDMAC (the N that 1500g crosses through anhydrous sodium sulfate drying is added in the four-hole boiling flask of condensing reflux and nitrogen protection device, N-dimethylacetylamide), nitrogen replaces 30 minutes, following mixture is dripped: 144.2g acrylic acid MA at 60 DEG C, 130.1g 2-hydroxyethyl methacry-late HEMA, 2g azodiisobutyronitrile AIBN, time for adding is 15 minutes, drip off rear reaction and within 5 hours, add 2gAIBN (azodiisobutyronitrile), react 5 hours again, then 13g benzyltrimethylammonium chloride TMBAC is added, 6.5g triphenylphosphine TPP, 6.5g NO free radical piperidine alcohols (ZJ701), 273.3g3, 4-epoxycyclohexyl-methyl acrylate CMA, react 2 hours at being warming up to 90 DEG C, react at being warming up to 110 DEG C again and terminate for 2 hours, reactant is separated out in the 10 liters of deionized waters adding 10g glacial acetic acid, then deionized water is fully washed, 40 DEG C of vacuum drying, obtain the molten unsaturated functional polymer adhesive a8 of branched hydroxy group alkali.Weight average molecular weight Mw=65400, iodine number Iv=70.0g iodine/100g resin, hydroxyl value Hv=102.5mgKOH/g resin, acid number Av=51.3mgKOH/g resin.
A compou nd synthesis example a9:
Temperature control heating is with at 3000ml, mechanical agitation, 1450gDMAC (the N that 1500g crosses through anhydrous sodium sulfate drying is added in the four-hole boiling flask of condensing reflux and nitrogen protection device, N-dimethylacetylamide), nitrogen replaces 30 minutes, following mixture is dripped: 180.2g acrylic acid MA at 60 DEG C, 45.5g 2-hydroxyethyl methacry-late HEMA, 2g azodiisobutyronitrile AIBN, time for adding is 15 minutes, drip off rear reaction and within 5 hours, add 2gAIBN (azodiisobutyronitrile), react 5 hours again, then 14g benzyltrimethylammonium chloride TMBAC is added, 7.0g triphenylphosphine TPP, 7.0g NO free radical piperidine alcohols (ZJ701), 282.3g GMA GMA, react 2 hours at being warming up to 90 DEG C, react at being warming up to 110 DEG C again and terminate for 2 hours, reactant is separated out in the 10 liters of deionized waters adding 10g glacial acetic acid, then deionized water is fully washed, 40 DEG C of vacuum drying, obtain the molten unsaturated functional polymer adhesive a9 of branched hydroxy group alkali.Weight average molecular weight Mw=83260, iodine number Iv=100.0g iodine/100g resin, hydroxyl value Hv=40.1mgKOH/g resin, acid number Av=55.2mgKOH/g resin.
A compou nd synthesis example a10:
Temperature control heating is with at 3000ml, mechanical agitation, 1700gDMAC (the N that 1500g crosses through anhydrous sodium sulfate drying is added in the four-hole boiling flask of condensing reflux and nitrogen protection device, N-dimethylacetylamide), nitrogen replaces 30 minutes, following mixture is dripped: 172.2g methacrylic acid MAA at 60 DEG C, 130.1g 2-hydroxyethyl methacry-late HEMA, 53.1g acrylonitrile AN, 2g azodiisobutyronitrile AIBN, time for adding is 15 minutes, drip off rear reaction and within 5 hours, add 2gAIBN (azodiisobutyronitrile), react 5 hours again, then 11g benzyltrimethylammonium chloride TMBAC is added, 5.5g triphenylphosphine TPP, 5.5g NO free radical piperidine alcohols (ZJ701), 213.2g GMA GMA, react 2 hours at being warming up to 90 DEG C, react at being warming up to 110 DEG C again and terminate for 2 hours, reactant is separated out in the 10 liters of deionized waters adding 10g glacial acetic acid, then deionized water is fully washed, 40 DEG C of vacuum drying, obtain the molten unsaturated functional polymer adhesive a10 of branched hydroxy group alkali.Weight average molecular weight Mw=78600, iodine number Iv=67.0g iodine/100g resin, hydroxyl value Hv=98.7mgKOH/g resin, acid number Av=49.3mgKOH/g resin.
A compou nd synthesis example a11:
Temperature control heating is with at 3000ml, mechanical agitation, 1720gDMAC (the N that 1500g crosses through anhydrous sodium sulfate drying is added in the four-hole boiling flask of condensing reflux and nitrogen protection device, N-dimethylacetylamide), nitrogen replaces 30 minutes, following mixture is dripped: 144.2g acrylic acid MA at 60 DEG C, 116.1g acrylic acid-2-hydroxyl ethyl ester HEA, 104.1g styrene St, 2g azodiisobutyronitrile AIBN, time for adding is 15 minutes, drip off rear reaction and within 5 hours, add 2gAIBN (azodiisobutyronitrile), react 5 hours again, then 14g benzyltrimethylammonium chloride TMBAC is added, 7.0g triphenylphosphine TPP, 7.0g NO free radical piperidine alcohols (ZJ701), 273.3g3, 4-epoxycyclohexyl-methyl acrylate CMA, react 2 hours at being warming up to 90 DEG C, react at being warming up to 110 DEG C again and terminate for 2 hours, reactant is separated out in the 10 liters of deionized waters adding 10g glacial acetic acid, then deionized water is fully washed, 40 DEG C of vacuum drying, obtain the molten unsaturated functional polymer adhesive a11 of branched hydroxy group alkali.Weight average molecular weight Mw=83200, iodine number Iv=59.7g iodine/100g resin, hydroxyl value Hv=87.9mgKOH/g resin, acid number Av=44.0mgKOH/g resin.
A compou nd synthesis example a12:
Temperature control heating is with at 3000ml, mechanical agitation, 1430gDMAC (the N that 1500g crosses through anhydrous sodium sulfate drying is added in the four-hole boiling flask of condensing reflux and nitrogen protection device, N-dimethylacetylamide), nitrogen replaces 30 minutes, following mixture is dripped: 77.4g methacrylic acid MAA at 60 DEG C, 116.1g acrylic acid-2-hydroxyl ethyl ester HEA, 156.2g styrene St, 79.7g acrylonitrile, 2g azodiisobutyronitrile AIBN, time for adding is 15 minutes, drip off rear reaction and within 5 hours, add 2gAIBN (azodiisobutyronitrile), react 5 hours again, then 3.6g benzyltrimethylammonium chloride TMBAC is added, 1.8g triphenylphosphine TPP, 1.8g NO free radical piperidine alcohols (ZJ701), 72.8g3, 4-epoxycyclohexyl-methyl acrylate CMA, react 2 hours at being warming up to 90 DEG C, react at being warming up to 110 DEG C again and terminate for 2 hours, reactant is separated out in the 10 liters of deionized waters adding 10g glacial acetic acid, then deionized water is fully washed, 40 DEG C of vacuum drying, obtain the molten unsaturated functional polymer adhesive a12 of branched hydroxy group alkali.Weight average molecular weight Mw=80180, iodine number Iv=20.0g iodine/100g resin, hydroxyl value Hv=111.7mgKOH/g resin, acid number Av=55.9mgKOH/g resin.
Synthesis b bis-urea ketone performed polymer: synthesis example b1-b5
Raw 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 vulcabond MDI: Mitsui chemistry; Toluene di-isocyanate(TDI) TDI: Japanese polyurethane industrial group; XDI XDI: Japanese Wu Tian pharmaceutical industries company, takenato; Naphthalene-1,5-vulcabond NDI: Mitsui Dong Ya KCC; Dicyclohexyl methyl hydride diisocyanate HMDI:Bayer, Desmodurw; MEK MEK: Japan improves petrochemical industry.
B compou nd synthesis example b1:
Temperature control heating is with at 2000ml, mechanical agitation, 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 vulcabond 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 NCO 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 agitation, 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 di-isocyanate(TDI) 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 NCO 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 agitation, 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 NCO 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 agitation, 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-vulcabond 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 NCO 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 agitation, 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 NCO 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 the dry coating weight of 1.8g/ ㎡.
Use above-mentioned a: the molten unsaturated functional polymer adhesive a1-a12 of branched hydroxy group alkali, b: two urea ketone performed polymers: synthesis example b1-b5 compound, makes heat susceptible coating containing a: the temperature-sensitive version embodiment 1-12 of the molten unsaturated functional polymer adhesive of branched hydroxy group alkali and b: two urea ketone performed polymers.
Embodiment 1-12:
(unit is g) to coating basic recipe
A sees attached list
B sees attached list
Two (the trichloromethyl)-s-triazine 0.1 of 2-(4-methoxyphenyl)-4,6-
Infrared absorbing agents ADS830AT0.1
Laurate diisobutyl tin 0.1
NO free radical piperidine alcohols 0.1
Alkaline bright blue 0.15
Surfactant (BYK306) 0.05
MEK 19.4
1-methoxy-2-propanol 70
Use above-mentioned a: the molten unsaturated functional polymer adhesive a1-a12 compound of branched hydroxy group alkali, base polyurethane prepolymer for use as uses Sartomer Sartomer399, make common temperature-sensitive version comparative example 1-12, comparative example temperature-sensitive version is simple radical polymerization temperature-sensitive version, not containing polyurethane heat cross-linking mechanism.
Comparative example 1-12:
Coating basic recipe (each component by weight)
A sees attached list
Sartomer399 sees attached list
Two (the trichloromethyl)-s-triazine 0.1 of 2-(4-methoxyphenyl)-4,6-
Infrared absorbing agents ADS830AT0.1
Laurate diisobutyl tin 0.1
NO free radical piperidine alcohols 0.1
Alkaline bright blue 0.15
Surfactant (BYK306) 0.05
MEK 19.4
1-methoxy-2-propanol 70
The above-mentioned protective layer of extrusion coated on above-mentioned plate, then at 120 DEG C dry 120 seconds, obtains the dry coating weight of 2.0g/ ㎡.
Protective layer 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
Plate performance is in table 1.
Table 1 plate application performance table
Remarks: loss 1 is the 80% butyl cellosolve aqueous solution/%, loss 2 is 50% isopropanol water solution/%.
Plate is evaluated:
Solvent resistance is investigated: above-mentioned plate sample to be immersed in respectively in butyl cellosolve 80% aqueous solution 20 minutes and isopropyl alcohol 50% aqueous solution 30 minutes, with sponge wiping cleaning, to measure plate coating loss.
Plate imaging performance is investigated: the all-victorious 800 thermo-sensitive platemaking machine plate-making of Kodak, Lekai China light produces the imaging of TPD-III developing liquid developing, MASTERVIEWMV-CTP washer, measures plate development adaptability and site performance.
Pressrun is investigated: normally printed (Heidelberg four look four drives high speed rotary press) by machine on above-mentioned plate sample, investigate its pressrun.
Shown by the detection application result of subordinate list, temperature-sensitive version of the present invention introduces brand-new thermographic mechanism, plate has free radical thermal polymerization and the dual thermographic ability of polyurethane heat cross-linking, polyurethane mesh heat cross-linking can be realized while realizing free radical linear polymerization, strong polarity ammonia ester bond has very high wearability, ammonia ester bond cross-linked network makes plate can obtain the pressrun of superelevation, exceeds much than traditional plate pressrun of single degree of freedom base polymerization thermographic.
Above-mentioned all embodiment plate development adaptability and site performance all meet print request.
Claims (8)
1. a long print journey temperature-sensitive version, is characterized in that: it comprises support and thermal polymerization layer, and wherein thermal polymerization layer mainly contains: the molten unsaturated functional polymer adhesive of branched hydroxy group alkali; Two urea ketone performed polymers; Thermal polymerization; Infrared absorbing agents; Organic metal promoter, the main chain of the molten unsaturated functional polymer adhesive of described branched hydroxy group alkali is at least containing 3 functional unit :-A-B-C-, wherein A: unsaturated functional unit: be carboxyl open loop substituent methyl glycidyl acrylate or 3,4-epoxycyclohexyl-methyl acrylate, B: branched hydroxy group functional unit: be 2-hydroxyethyl methacry-late or acrylic acid-2-hydroxyl ethyl ester, C: the molten functional unit of alkali: be methacrylic acid or acrylic acid, described two urea ketone performed polymers have following general structure:
Wherein, the structural formula of R is:
,
,
,
or
.
2. long print journey temperature-sensitive version according to claim 1, is characterized in that: described support is the aluminum substrate through electrolytic graining, anodic oxidation and hole-sealing treatment process, and Grains center line average boldness is 0.3-0.6 μm.
3. long print journey temperature-sensitive version according to claim 1, is characterized in that: described thermal polymerization is peroxide, azo compound, salt compounds or the triaizine compounds containing halogen substiuted.
4. long print journey temperature-sensitive version according to claim 1, is characterized in that: the cyanine dyes of described infrared absorbing agents to be absorption maximum scope be 760-1200nm.
5. long print journey temperature-sensitive version according to claim 1, is characterized in that: described organic metal promoter is the compound of mercury, lead, tin, bismuth, zinc, iron.
6. the long print journey temperature-sensitive version according to claim 1 or 3, it is characterized in that: the molten unsaturated functional polymer adhesive weight average molecular weight of described branched hydroxy group alkali is 20,000-10 ten thousand, iodine number Iv=20-100g iodine/100g resin, hydroxyl value is 100-180mgKOH/g resin, and acid number is 20-120mgKOH/g resin.
7. long print journey temperature-sensitive version according to claim 1, is characterized in that: the molten unsaturated functional polymer adhesive a of branched hydroxy group alkali and two urea ketone performed polymer b, a component accounts for a, and the 50-90% of b gross weight, b component accounts for a, the 10-50% of b gross weight.
8. long print journey temperature-sensitive version according to claim 1, is characterized in that: also comprise solvent, normal temperature thermal polymerization inhibitor, coating colours, surfactant addO-on therapy in thermal polymerization layer.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1359031A (en) * | 2000-12-11 | 2002-07-17 | 富士胶片株式会社 | Original plate for lithographic printing plate |
| CN1378918A (en) * | 2001-04-03 | 2002-11-13 | 富士胶片株式会社 | Supporting body for lithographic plate and lithographic original plate |
| CN1688441A (en) * | 2002-10-15 | 2005-10-26 | 爱克发-格法特公司 | Heat-sensitive lithographic printing plate precursor |
| EP1101607B1 (en) * | 1999-11-19 | 2006-06-07 | Kodak Polychrome Graphics Company Ltd. | Article having imageable coatings |
| CN101253054A (en) * | 2005-08-30 | 2008-08-27 | 柯尼卡美能达医疗印刷器材株式会社 | Printing plate material and process for producing printing plate |
| EP1698218A4 (en) * | 2003-11-27 | 2010-01-20 | Fujifilm Corp | Metal pattern forming method, metal pattern obtained by the same, printed wiring board, conductive film forming method, and conductive film obtained by the same |
| CN101852991A (en) * | 2009-03-31 | 2010-10-06 | 富士胶片株式会社 | Photosensitive composition, photosensitive film, photosensitive laminated body, permanent pattern forming method and printed board |
| CN102617445A (en) * | 2007-07-17 | 2012-08-01 | 富士胶片株式会社 | Photosensitive compositions, curable compositions, novel compounds, photopolymerizable compositions, color filters, and planographic printing plate precursors |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012177716A (en) * | 2011-02-25 | 2012-09-13 | Toyo Ink Sc Holdings Co Ltd | Red colored composition for color filter |
-
2012
- 2012-12-21 CN CN201210560864.XA patent/CN103879168B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1101607B1 (en) * | 1999-11-19 | 2006-06-07 | Kodak Polychrome Graphics Company Ltd. | Article having imageable coatings |
| CN1359031A (en) * | 2000-12-11 | 2002-07-17 | 富士胶片株式会社 | Original plate for lithographic printing plate |
| CN1378918A (en) * | 2001-04-03 | 2002-11-13 | 富士胶片株式会社 | Supporting body for lithographic plate and lithographic original plate |
| CN1688441A (en) * | 2002-10-15 | 2005-10-26 | 爱克发-格法特公司 | Heat-sensitive lithographic printing plate precursor |
| EP1698218A4 (en) * | 2003-11-27 | 2010-01-20 | Fujifilm Corp | Metal pattern forming method, metal pattern obtained by the same, printed wiring board, conductive film forming method, and conductive film obtained by the same |
| CN101253054A (en) * | 2005-08-30 | 2008-08-27 | 柯尼卡美能达医疗印刷器材株式会社 | Printing plate material and process for producing printing plate |
| CN102617445A (en) * | 2007-07-17 | 2012-08-01 | 富士胶片株式会社 | Photosensitive compositions, curable compositions, novel compounds, photopolymerizable compositions, color filters, and planographic printing plate precursors |
| CN101852991A (en) * | 2009-03-31 | 2010-10-06 | 富士胶片株式会社 | Photosensitive composition, photosensitive film, photosensitive laminated body, permanent pattern forming method and printed board |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109839803A (en) * | 2019-01-25 | 2019-06-04 | 安徽强邦印刷材料有限公司 | A kind of heat susceptible coating for exempting from processing CTP editions suitable for water development |
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| CN103879168A (en) | 2014-06-25 |
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Effective date of registration: 20220316 Address after: 473003 No. 718 South Station Road, Wolong District, Henan, Nanyang Patentee after: Lucky Huaguang Graphics Co.,Ltd. Patentee after: Henan Huafu Packaging Technology Co., Ltd Address before: 473003 No. 718 South Station Road, Henan, Nanyang Patentee before: Lucky Huaguang Graphics Co.,Ltd. |