CN102030855B - Urethanated unsaturated water-soluble vinyl multipolymer and preparation method thereof - Google Patents
Urethanated unsaturated water-soluble vinyl multipolymer and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an urethanated unsaturated water-soluble vinyl multipolymer and a preparation method thereof. The urethanated unsaturated water-soluble vinyl multipolymer is a vinyl multipolymer containing the following structure unit: -A-B-C (-X)-D-, wherein A represents a styrene structure unit; B represents a (methyl) acrylonitrile structure unit; C represents a vinyl copolymerization unit containing branched hydroxyl; D represents a vinyl copolymerization unit containing a branched hydrophilic group; and X represents a C unit branched hydroxyl grafted unsaturated mono isocyanate structure unit. The polymer is applicable to manufacturing chemistry-free CTP boards.
Description
Technical field
The invention belongs to printing technology, be specifically related to the unsaturated water soluble vinyl multiple copolymer of a kind of ammonia esterification and synthetic method thereof.
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 universal gradually.CTP plate kind is a lot, relatively universal Silver Salt Diffusion Transfer CTP Plate material, UV-CTP version, purple laser polymerization CTP plate, the thermal CTP plate material etc. of comprising.At present, the focus of chemical treatment CTPBan Shi world plate exploitation is exempted from Development of New Generation environmental protection.
It is a lot of that chemical treatment CTP platemaking technology route is exempted from exploitation environmental protection, can be divided into thermal ablation technology, polarity conversion technology and hot-melt technology.Thermal ablation technology plate adopts aluminium plate base or polyester based, utilizes plasma metal deposition technique to prepare plate.But there is residue problem in ablation plate.Presstek company has delivered the ablation plate with sandwich structure, has solved ablation residue problem.Agfa Corp. develops the ablation technology non-processor CTP version with deposited silver layer, and this plate is by having the support (aluminium, PET) of water-wetted surface, metal deposition layer and crosslinked hydrophobic layer formation that can be ablated.Metal deposition layer is the metallic membrane that utilizes metal deposition technique to form, and this metal can be silver, titanium etc.Crosslinked hydrophobic layer, by radiation or thermofixation, makes unsaturated monomer crosslinked, also can be cross-linked to form cured layer by heat-sensitive resin, maybe can be processed and be obtained by sense fat liquid.Infrared laser power causes that capillary variation occurs the silver-colored particle in silver layer, form fluffy silver-colored particle, remain on plate surface, thereby be easy to remove residue with vacuum suck 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 comprised of support and thermographic layer.Thermographic layer contains photo-thermal and changes agent and the convertible polymkeric substance of temperature-sensitive (as poly-tetrahydropyrans methacrylic ester, with aryl diazosulfonic acid base ethylene copolymer).Adopt the convertible polymer formation thermo-sensitive material of temperature-sensitive.Before imaging, the water-soluble solution of heat-sensitive layer.During imaging, infrared absorbing agents absorbing laser energy, the heat of generation causes that diazo decomposes, make to be exposed temperature-sensitive multipolymer from hydrophilic become hydrophobic, thereby form oleophylic district.And unexposed area temperature-sensitive multipolymer is still water-soluble, thereby form hydrophilic area.The factor that restricts this technical development remains printability.Its ink part is all medicine film coating, and printing is controlled with pressrun and is all subject to severely restricts, realizes real large-scale commercial application and also has larger distance.
Hot-melt technology: the technology that is real Commercialization application in current third generation processless CTP.It is the technology of Agfa Corp.'s exploitation.The agent of thermographic middle infrared absorption is converted into heat energy laser energy, the temperature that the heat producing makes to be dispersed in the thermoplastic polymer particles in crosslinked hydrophilic layer is higher than its gel humidity, cause thermoplastic polymer particles generation agglutination reaction, exposure region becomes hydrophobic lipophilicity by wetting ability.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 oxide treatment, rather than medicine film coating, and printability and common plate are without any difference.
Chemical treatment CTP version is exempted from exploitation, and one of gordian technique is that plate precursor is the organic exploitation of function.EP0980754 has introduced carboxyl decarboxylation and has realized hydrophilic hydrophobic conversion techniques, but phase fluxional compounnd molecular weight is too large, and it is large that energy threshold becomes, and decarboxylation difficulty, so this technology plate pressrun is poor.WO94/23954 has introduced a kind of microcapsule hot-melt technology, and laser hot melt destroys microcapsule, 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 thermoplasticity hydrophobic granule and hydrophilic adhesive, but not resistance to seal; Ai Kefa EP 2006-5-24 06114475.4, CN200780018820 introduce a kind of semicontinuous emulsion method and manufacture vinylbenzene, acrylonitrile emulsion thermoplastic granulates, can realize hot melt, but not containing self-emulsifying hydrophilic radical, particle control techniques requires high, emulsification stability of emulsion is poor, need add anti-micro-raw agent; The US 2005-8-3 of Kodak 11/196,124, CN200680028684 introduce a kind of tackiness agent that comprises polyalkylene oxide hydrocarbon segment and the polymerization of hydrophobic cyano group side group, and molecule is one-dimensional linear structure,, containing two keys, can not participate in plate crosslinked, so pressrun is influenced; The US 2006-7-27 of Kodak 11/494,235, CN200780028508 introduces a kind of thing of resistance to solvent polymeric containing hydrophilic group and cyano group side group, 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 trouble, and ester group not resistance to seal still; Fujiphoto JP 2000-7-13 2000-213142, CN01120259 introduce a kind of Lighographic printing plate precursor, the polymkeric substance that contains three-dimensional polyisocyanates precrosslink structure and comprise hydrophilic grafted chain, though three-dimensional precrosslink structure has improved plate pressrun, reduced plate in machine developability.
Summary of the invention
The object of the invention is to solve the above-mentioned shortcoming existing in prior art, the unsaturated water soluble vinyl multiple copolymer of a kind of ammonia esterification and synthetic method thereof are provided, a kind of chemical treatment CTP plate precursor of better exempting from is provided.
For achieving the above object, the present invention adopts following technical scheme:
The unsaturated water soluble vinyl multiple copolymer of ammonia esterification of the present invention, it is the vinyl multiple copolymer that contains following structural unit:
-A-B-C(-X)-D-
A represents styrol structural unit, is thermoplastic structure unit.
B representative (methyl) acrylonitrile unit unit is hydrophobic nature structural unit.
C representative, containing the vinyl copolymerization units of branched hydroxy group, is the bridge of grafting ammonia esterification vinyl.
D representative, containing the vinyl copolymerization units of side chain hydrophilic group, is hydrophilic-structure unit.
X represents the unsaturated monoisocyanates structural unit of C unit branched hydroxy group grafting, for being cross-linked into picture structural unit.
The weight-average molecular weight of multipolymer of the present invention is 5000-200000; Glass transition temperature is 30-260 ℃; The weight percent content of styrene copolymerized unit A in grafting multiple copolymer is not 30-80%; The weight percent content of (methyl) acrylonitrile compolymer unit B in grafting multiple copolymer is not 0.5%-40%; Containing the vinyl copolymerization units C of branched hydroxy group, at the weight percent content in grafting multiple copolymer not, be 0.5%-40%; Containing the vinyl copolymerization units D of side chain hydrophilic radical, at the weight percent content in grafting multiple copolymer not, be 0.5%-40%.
The weight-average molecular weight of multipolymer of the present invention is preferably 15000-100000; Glass transition temperature is preferably 40-150 ℃; The weight percent content of styrene copolymerized unit A in grafting multiple copolymer is not preferably 40-70%; The weight percent content of (methyl) acrylonitrile compolymer unit B in grafting multiple copolymer is not preferably 5%-30%; Containing the vinyl copolymerization units C of branched hydroxy group, at the weight percent content in grafting multiple copolymer not, be preferably 5-30%; Containing the vinyl copolymerization units D of side chain hydrophilic radical, at the weight percent content in grafting multiple copolymer not, be preferably 5-30%.
The weight-average molecular weight of multipolymer of the present invention most preferably is 40000-80000; Glass transition temperature most preferably is 60-130 ℃; The weight percent content of styrene copolymerized unit A in grafting multiple copolymer most not preferably is 50-60%; The weight percent content of (methyl) acrylonitrile compolymer unit B in grafting multiple copolymer most not preferably is 10-20%; Containing the vinyl copolymerization units C of branched hydroxy group, at the weight percent content in grafting multiple copolymer not, most preferably be 10-20%; Containing the vinyl copolymerization units D of side chain hydrophilic radical, at the weight percent content in grafting multiple copolymer not, most preferably be 10-20%.
The structural formula of the unsaturated monoisocyanates structural unit X of described C unit branched hydroxy group grafting is:
In formula, R
1for hydrogen atom or methyl, R
2for ester group, penylene base or valence link, the integer that r is 1-3; The molar ratio of unsaturated monoisocyanates X and vinyl copolymerization units C institute hydroxyl is 0.1-1.0.
The molar ratio of the unsaturated monoisocyanates X of described C unit branched hydroxy group grafting and vinyl copolymerization units C institute hydroxyl is preferably 0.5-1.00.
Described is at least one of carboxyl, amide group, sulfonic group, phosphate or ether containing hydrophilic radical in the vinyl copolymerization units D of side chain hydrophilic radical.
The synthetic method of the unsaturated water soluble vinyl multiple copolymer of ammonia esterification of the present invention is: first carry out synthesize-A-B-C-D-multiple copolymer of multi-component copolymer reaction, then by C unit branched hydroxy group and insatiable hunger monoisocyanates X ammonia esterification grafting unsaturated double-bond.
Reaction solvent adopts any one in ammonia ester level dimethyl formamide, N,N-DIMETHYLACETAMIDE or methylethylketone.
The catalyzer of described ammonia graft esterification reaction is lead octoate 36, stannous octoate, dibutyl tin laurate, triethylenediamine, cobalt octoate or iron octoate, and consumption is the 0.005-10% of unsaturated monoisocyanates monomer weight of feeding intake; Graft reaction temperature is 40-120 ℃; Stopper is a kind of in Resorcinol, para benzoquinone, toluhydroquinone, MEHQ, 2-Tert. Butyl Hydroquinone, 2,5 di tert butyl hydroquinone, nitroxyl free radical piperidine alcohols.
The catalyzer of described ammonia graft esterification reaction is preferably dibutyl tin laurate, and consumption is preferably the 0.05-5% of the unsaturated monoisocyanates monomer weight that feeds intake; Graft reaction temperature is preferably 60-90 ℃, and stopper is preferably nitroxyl free radical piperidine alcohols.
Multipolymer of the present invention is a kind of one-dimensional linear multiple copolymer, and it comprises as dominance structure unit: 1,, containing thermoplastic structure unit, multipolymer, as exempting from chemical treatment heat-sensitive CTP plate tackiness agent, has good thermoplasticity; 2, contain cyano group side group hydrophobic group, multipolymer, as tackiness agent crosslink part, has good resistance, snappiness and hydrophobic nature; 3, contain water soluble group, multipolymer has good wetting ability as the uncrosslinked part of tackiness agent, can realize water or natural gum development; 4, contain the unsaturated crosslinked group of vinyl, and polyfunctional group performed polymer can form 3-D solid structure after crosslinked, the transformation of plate from hydrophilic to hydrophobic is more obvious, and plate is also more wear-resisting than adding precrosslink 3-D solid structure tackiness agent; 5, contain polyurethane structural, better with base polyurethane prepolymer for use as intermiscibility, good film-forming property, plate is not prone to the appearance that causes spot because of film-forming components dissolubility difference, and plate is also more wear-resisting.
Great majority are exempted from chemical treatment heat-sensitive CTP plate tackiness agent and have all been designed thermoplastic styrene structural unit, and multiple copolymer of the present invention is also containing thermoplastic styrene structural unit A.As everyone knows, styrol structural unit has good thermoplasticity, glass transition temp is higher, styrol copolymer has the easier hot melt of heated portion as exempting from chemical treatment heat-sensitive CTP plate tackiness agent, between molecule, arrange more tight, thermal imagery part is more firm, can increase the advantage of plate pressrun.The content of vinylbenzene in multiple copolymer directly affects glass transition temperature and the thermoplasticity of polymkeric substance.Synthetic multiple copolymer of the present invention, styrene copolymerized unit A weight percent content in grafting multiple copolymer is not 30-80%, preferably 40-70%, is preferably 50-60%.
Design a kind of CTP version tackiness agent, it is necessary selecting outstanding hydrophobic segment.Cyano group is more outstanding hydrophobic group.Multiple copolymer of the present invention is introduced hydrophobic side chain cyano group, and multipolymer is introduced after hydrophobic side chain cyano group, as the crosslinked imaging moiety of tackiness agent, has good snappiness, resistance and hydrophobic nature.The method that multiple copolymer of the present invention is introduced hydrophobic side chain radical nitrile is in copolymerization component, to have designed the vinyl component structure unit B of side chain containing base nitrile, it comprises Methyl 2-cyanoacrylate, cyanacrylate, vinyl cyanide or methacrylonitrile etc., preferably vinyl cyanide or methacrylonitrile or their mixture.Synthetic multiple copolymer of the present invention, (methyl) acrylonitrile compolymer unit B weight percent content in grafting multiple copolymer is not 0.5%-40%, preferably 5%-30%, is preferably 10-20%.
As exempting from chemical treatment CTP version tackiness agent, it is relatively good that resin contains unsaturated group, and resin is crosslinked with polyfunctionality performed polymer under the effect of light or heat, form three-dimensional crosslinking structure, resin can be realized polarity and deliquescent change, by hydrophilic, changes into hydrophobicly, realizes plate imaging printing.The method that resin is introduced two keys has a lot, can adopt side chain carboxyl, hydroxyl, amino or epoxy group(ing) etc. by reactive grafting vinyl monomers such as condensation or open loops, but the method side reaction and by product is more, aftertreatment trouble.Also can adopt group that side chain contains active hydrogen if hydroxyl, amido etc. and the monoisocyanates that contains vinyl are by hydrogen transfer reactions grafting unsaturated double-bond, the method is almost without side reaction and by product, and product can directly be used without aftertreatment.As everyone knows, the tackiness agent that contains strong polarity ammonia ester bond has very strong adsorption to aluminium plate base, can improve the pressrun of plate.In addition, better containing tackiness agent and the base polyurethane prepolymer for use as intermiscibility of polyurethane structural, plate is not prone to the appearance that causes pepper point because of film-forming components dissolubility difference, and plate apparent property is even more ideal.So multiple copolymer of the present invention is also introduced ammonia esterification unsaturated double-bond.The monoisocyanates reactive grafting unsaturated double-bond that multiple copolymer synthetic of the present invention adopts branched hydroxy group and contains vinyl.Multiple copolymer of the present invention has designed the structure copolymerization units C containing branched hydroxy group, as the bridge of graft reaction.C can be containing monohydroxy, dihydroxyl or polyhydric vinyl copolymerization units.
Containing side chain monohydroxy vinyl copolymerization units, typically have hydroxyethyl methylacrylate, Hydroxyethyl acrylate, Rocryl 410, vinylformic acid-2-hydroxyl-3-phenoxy group propyl ester, 4-Vinyl phenol, to methylol vinylbenzene etc., preferable methyl Hydroxyethyl acrylate, Hydroxyethyl acrylate, most preferable Hydroxyethyl acrylate.
Containing the concrete example of the dihydric vinyl copolymerization units of side chain C as:
C1
C2
C3
C4
Containing two or the vinyl monomer of higly branched chain hydroxyl be mostly vinyl monomer and containing two or the compound reaction of higly branched chain hydroxyl obtain ester, ether, amine or amides condensed products, be generally laboratory sintetics, because of its consumption little, seldom there is industrialization product, so synthetic multiple copolymer of the present invention does not adopt this type of monomer as far as possible, but this type of monomer is for polymer performance, exploration is helpful.
Synthetic multiple copolymer of the present invention, is 0.5-40% containing the vinyl copolymerization units C of branched hydroxy group weight percent content in grafting multiple copolymer not, and preferably 5%-30%, is preferably 10-20%.
Synthetic polymer graft of the present invention unsaturated monoisocyanates X structural formula used is:
R
1for hydrogen atom or methyl, R
2for ester group, penylene base or valence link etc., the integer that r is 1-3.
Detailed example is shown in following structural formula, but the present invention is not limited to the structural formula of following X1-X3.
X1
X2
X3
Polymkeric substance ammonia graft esterification reaction synthetic of the present invention, unsaturated monoisocyanates and C unit hydroxyl molar ratio 0.1-1.0, optimum is 0.5-1.0, the best is 0.9.
As the tackiness agent of exempting from chemical treatment CTP version, it is relatively good that resin contains water soluble group, the resin of containing water-soluble group is as the tackiness agent of exempting from chemical treatment heat-sensitive CTP plate, uncrosslinked part can realize water or the simple precleaning of natural gum, or at machine, be printed on and under the effect of fountain solution, realize cleanly, expose hydrophilic version base, and the crosslinked imaging moiety that is heated is because tackiness agent and performed polymer are cross-linked to form three-dimensional structure, polarity and solvability change, by hydrophilic change into hydrophobic.Realizing the water miscible best approach of resin is exactly directly to select to have the vinyl monomer of hydrophilic side group as the copolymerization units of resin.Hydrophilic side group has carboxyl, hydroxyl, phosphate, sulfonic group, amino, amide group, ether etc.But synthetic the present invention is described water-soluble multiple copolymer, pendant hydrophilic group must be discord isocyanic ester radical reaction, or and isocyanate reaction specific activity hydroxyl reaction and isocyanate reaction activity weak many pendant hydrophilic groups, water-soluble to avoid reducing resin with the monoisocyanates unsaturated monomer reaction of grafting.Optional water soluble group is carboxyl, amide group, sulfonic group, phosphate, ether etc., preferred wetting ability side group is amide group, sulfonic group, ether (comprising polyethoxye) or their combination, as acryloyl morpholine, 2-acrylamide-2-methacrylic sulfonic acid CH
2=CHCONHC (CH
3) CH
2sO
3h, methoxy polyethylene glycol acrylate CH
3o(CH
2cH
2o) nOCCH=CH
2deng.If select side chain to contain the water-soluble monomer of polyethoxye, polyethoxye molecular weight can not be too large, otherwise main chain copolyreaction is affected, and molecular weight is too little water-soluble too poor.Effective molecular weight is 400-10000, preferably 1000-50000, particularly preferably 1500-20000.
Synthetic multiple copolymer of the present invention, is 0.5-30% containing the vinyl copolymerization units D of side chain hydrophilic radical weight percent content in grafting multiple copolymer not, and preferably 5%-30%, is preferably 10-20%.
The method of the synthetic unsaturated water soluble vinyl multiple copolymer of ammonia esterification of the present invention is, first carry out synthesize-A-B-C-D-multiple copolymer of multi-component copolymer reaction, then by the unsaturated monoisocyanates structural unit of C unit branched hydroxy group ammonia esterification grafting.
The optional random copolymerization of main chain resin copolyreaction or block copolymerization, preferably random copolymerization.The initiator of polymerization comprises that superoxide is as ditertiary butyl peroxide, benzoyl peroxide; persulphate is if Potassium Persulphate, azo-compound are as Diisopropyl azodicarboxylate etc.; reaction can adopt letex polymerization, suspension polymerization or solution polymerization, preferably adopts solution polymerization.Reaction can adopt single stage method or two-step approach to complete, preferably adopt single stage method synthetic, adopt single stage method, but reaction solvent must be not contain the solvent of active proton hydrogen, as 1,4-dioxane, DMF, N,N-DIMETHYLACETAMIDE, methylethylketone, pimelinketone, ethyl acetate, toluene etc., or their mixture.Preferably adopt ammonia ester level dimethyl formamide, N,N-DIMETHYLACETAMIDE or pimelinketone.Copolyreaction temperature 40-110 ℃, is preferably in 50-100 ℃.
The catalyzer of the unsaturated monoisocyanates of grafting all can as lead octoate 36, stannous octoate, dibutyl tin laurate, triethylenediamine, cobalt octoate, iron octoate etc., dibutyl tin laurate preferably, consumption is the 0.005-10% of unsaturated monoisocyanates monomer weight of feeding intake, and optimum quantity is 0.05-5%.Graft reaction temperature 40-120 ℃, is preferably in 60-110 ℃.The stopper adopting is Resorcinol HQ, para benzoquinone PBQ, toluhydroquinone THQ, MEHQ HQMME, 2-Tert. Butyl Hydroquinone MTBHQ, 2,5-di-tert-butyl hydroquinone 2,5-DTBHQ, nitroxyl free radical piperidine alcohols ZJ-701 etc., preferably adopt nitroxyl free radical piperidine alcohols ZJ-701.
The weight-average molecular weight of the unsaturated water soluble vinyl multiple copolymer of ammonia esterification of the present invention is 5000-200000, is preferably 15000-10000, most preferably is 40000-80000.Glass transition temperature is 30-260 ℃, is preferably 40-150 ℃, most preferably is 60-130 ℃.
The unsaturated water soluble vinyl multiple copolymer of ammonia esterification of the present invention, its purposes is to manufacture to exempt from chemical treatment CTP version.
Embodiment
Be synthetic example of the present invention below, but the present invention is not limited to following example.
Embodiment 1(copolymer A)
At 1000 ml band temperature control heatings, mechanical stirring, in the four-hole boiling flask of condensing reflux and nitrogen protection device, add the DMF (N that 500 g cross through anhydrous sodium sulfate drying, dinethylformamide) and 120.0g (60 % by weight) SM (vinylbenzene), 40.0g (20 % by weight) AN (vinyl cyanide), 20.0g (10 % by weight) HEMA (hydroxyethyl methylacrylate), 20.0g (10 % by weight) AMPS (2-acrylamide-2-methacrylic sulfonic acid), nitrogen protects heated and stirred and add 1.0gAIBN (Diisopropyl azodicarboxylate) to dissolution of solid, 70 ℃ of reactions were added 0.5gAIBN after 3 hours, react again after 4 hours and add dibutyl tin laurate 0.1g, 23.8gMOI (X2 example compound), ZJ-701(nitroxyl free radical piperidine alcohols) 0.1g, after 1 hour, reaction finishes.
Solid content is 30.9% weight, GPC weight-average molecular weight Mw=57900, iodine number Iv=17.4gI2/100g resin.
Embodiment 2(multipolymer B)
At 1000 ml band temperature control heatings, mechanical stirring, in the four-hole boiling flask of condensing reflux and nitrogen protection device, add dioxane and 110.0g (55 % by weight) SM (vinylbenzene) that 500 g cross through anhydrous sodium sulfate drying, 30.0g (15 % by weight) MAN (methacrylonitrile), 30.0g (15 % by weight) Hydroxyethyl acrylate, 30.0g (15 % by weight) acryloyl morpholine, nitrogen protects heated and stirred and add 1.0gAIBN (Diisopropyl azodicarboxylate) to dissolution of solid, 90 ℃ of reactions were added 0.5gAIBN after 3 hours, react again after 4 hours and add dibutyl tin laurate 0.1g, 40.1gMOI (X2 example compound), ZJ-701(nitroxyl free radical piperidine alcohols) 0.1g, after 1 hour, reaction finishes.
Solid content is 32.4% weight, GPC weight-average molecular weight Mw=63400, iodine number Iv=22.3gI2/100g resin.
Embodiment 3(multipolymer C)
At 1000 ml band temperature control heatings, mechanical stirring, in the four-hole boiling flask of condensing reflux and nitrogen protection device, add ethyl acetate and 120.0g (60 % by weight) SM (vinylbenzene) that 500g crosses through anhydrous sodium sulfate drying, 40.0g (20 % by weight) AN (Methyl 2-cyanoacrylate), 20.0g (10 % by weight) Rocryl 410, 20.0g (10 % by weight) PEGMA (methoxy polyethylene glycol methacrylate-styrene polymer, Mn=2040) nitrogen protects heated and stirred and adds 1.0gAIBN (Diisopropyl azodicarboxylate) after evenly, 40 ℃ of reactions were added 0.5gAIBN after 3 hours, react again after 4 hours and add lead octoate 36 0.1g, 21.5gMOI (X2 example compound), ZJ-701(nitroxyl free radical piperidine alcohols) 0.1g, after 1 hour, reaction finishes.
Solid content is 30.7% weight, GPC weight-average molecular weight Mw=31300, iodine number Iv=16.4gI2/100g resin.
Embodiment 4(multipolymer D)
At 1000 ml band temperature control heatings, mechanical stirring, in the four-hole boiling flask of condensing reflux and nitrogen protection device, add N,N-DIMETHYLACETAMIDE and 110.0g (55 % by weight) SM (vinylbenzene) that 500g crosses through anhydrous sodium sulfate drying, 30.0g (15 % by weight) MAN (cyanacrylate), 30.0g (15 % by weight) vinylformic acid-2-hydroxyl-3-phenoxy group propyl ester, 30.0g (15 % by weight) PEGMA (methoxy polyethylene glycol methacrylate-styrene polymer, Mn=2040), nitrogen protects heated and stirred and adds 1.0gAIBN (Diisopropyl azodicarboxylate) after evenly, 80 ℃ of reactions were added 0.5gAIBN after 3 hours, react again after 4 hours and add stannous octoate 0.1g, 20.9gMOI (X2 example compound), ZJ-701(nitroxyl free radical piperidine alcohols) 0.1g, after 1 hour, reaction finishes.
Solid content is 30.6% weight, GPC weight-average molecular weight Mw=72800, iodine number Iv=15.5gI2/100g resin.
Embodiment 5(multipolymer E)
At 1000 ml band temperature control heatings, mechanical stirring, in the four-hole boiling flask of condensing reflux and nitrogen protection device, add pimelinketone and 110.0g (55 % by weight) SM (vinylbenzene) that 500g crosses through anhydrous sodium sulfate drying, 30.0g (15 % by weight) AN (vinyl cyanide), 20.0g (10 % by weight) 4-Vinyl phenol, 40.0g (20 % by weight) ACMO (acrylamide morpholine), nitrogen protects heated and stirred and adds 1.0gAIBN (Diisopropyl azodicarboxylate) after evenly, 120 ℃ of reactions were added 0.5gAIBN after 3 hours, react again after 4 hours and add triethylenediamine 0.1g, 25.8g (0.10mol), MOI (X2 example compound) 1.0g, ZJ-701(nitroxyl free radical piperidine alcohols) 0.1g, after 1 hour, reaction finishes.
Solid content is 31.1% weight, GPC weight-average molecular weight Mw=61700, iodine number Iv=18.7gI2/100g resin.
Embodiment 6(multipolymer F)
At 1000 ml band temperature control heatings, mechanical stirring, in the four-hole boiling flask of condensing reflux and nitrogen protection device, add toluene and 160.0g (80 % by weight) SM (vinylbenzene) that 500 g cross through anhydrous sodium sulfate drying, 1.0g(0.5 % by weight) AN (vinyl cyanide), 10.0g (5 % by weight) HEMA (hydroxyethyl methylacrylate), 29.0g (14.5 % by weight) AMPS (2-acrylamide-2-methacrylic sulfonic acid), nitrogen protects heated and stirred and add 1.0gAIBN (Diisopropyl azodicarboxylate) to dissolution of solid, 100 ℃ of reactions were added 0.5gAIBN after 3 hours, react again after 4 hours and add cobalt octoate 0.1g, 11.9gMOI (X2 example compound), ZJ-701(nitroxyl free radical piperidine alcohols) 0.1g, after 1 hour, reaction finishes.
Solid content is 29.8% weight, GPC weight-average molecular weight Mw=64900, iodine number Iv=9.2gI2/100g resin.
Embodiment 7(multipolymer G)
At 1000 ml band temperature control heatings, mechanical stirring, in the four-hole boiling flask of condensing reflux and nitrogen protection device, add pimelinketone and 140.0g (70 % by weight) SM (vinylbenzene) that 500 g cross through anhydrous sodium sulfate drying, 10.0g (5 % by weight) AN (vinyl cyanide), 1.0g (0.5 % by weight) HEMA (hydroxyethyl methylacrylate), 24.5g (10 % by weight) AMPS (2-acrylamide-2-methacrylic sulfonic acid), nitrogen protects heated and stirred and add 1.0gAIBN (Diisopropyl azodicarboxylate) to dissolution of solid, 110 ℃ of reactions were added 0.5gAIBN after 3 hours, react again after 4 hours and add dibutyl tin laurate 0.1g, 1.2gMOI (X2 example compound), ZJ-701(nitroxyl free radical piperidine alcohols) 0.1g, after 1 hour, reaction finishes.
Solid content is 28.7% weight, GPC weight-average molecular weight Mw=59600, iodine number Iv=1.0gI2/100g resin.
Embodiment 8(multipolymer H)
At 1000 ml band temperature control heatings, mechanical stirring, in the four-hole boiling flask of condensing reflux and nitrogen protection device, add the DMF (N that 500 g cross through anhydrous sodium sulfate drying, dinethylformamide) and 100.0g (50 % by weight) SM (vinylbenzene), 60.0g (30 % by weight) AN (vinyl cyanide), 39.0g (19.5 % by weight) HEMA (hydroxyethyl methylacrylate), 1.0g (0.5 % by weight) AMPS (2-acrylamide-2-methacrylic sulfonic acid), nitrogen protects heated and stirred and add 1.0gAIBN (Diisopropyl azodicarboxylate) to dissolution of solid, 70 ℃ of reactions were added 0.5gAIBN after 3 hours, react again after 4 hours and add dibutyl tin laurate 0.1g, 46.4gMOI (X2 example compound), ZJ-701(nitroxyl free radical piperidine alcohols) 0.1g, after 1 hour, reaction finishes.
Solid content is 33.0% weight, GPC weight-average molecular weight Mw=57400, iodine number Iv=30.8gI2/100g resin.
Embodiment 9(multipolymer I)
At 1000 ml band temperature control heatings, mechanical stirring, in the four-hole boiling flask of condensing reflux and nitrogen protection device, add the DMF (N that 500 g cross through anhydrous sodium sulfate drying, dinethylformamide) and 80.0g (40 % by weight) SM (vinylbenzene), 20.0g (10 % by weight) AN (vinyl cyanide), 20.0g (10 % by weight) HEMA (hydroxyethyl methylacrylate), 80.0g (40 % by weight) AMPS (2-acrylamide-2-methacrylic sulfonic acid), nitrogen protects heated and stirred and add 1.0gAIBN (Diisopropyl azodicarboxylate) to dissolution of solid, 70 ℃ of reactions were added 0.5gAIBN after 3 hours, react again after 4 hours and add dibutyl tin laurate 0.1g, 23.8gMOI (X2 example compound), ZJ-701(nitroxyl free radical piperidine alcohols) 0.1g, after 1 hour, reaction finishes.
Solid content is 30.9% weight, GPC weight-average molecular weight Mw=59100, iodine number Iv=17.4gI2/100g resin.
Embodiment 10(multipolymer J)
At 1000 ml band temperature control heatings, mechanical stirring, in the four-hole boiling flask of condensing reflux and nitrogen protection device, add the DMF (N that 500 g cross through anhydrous sodium sulfate drying, dinethylformamide) and 60.0g (30 % by weight) SM (vinylbenzene), 20.0g (10 % by weight) AN (vinyl cyanide), 60.0g (30 % by weight) HEMA (hydroxyethyl methylacrylate), 60.0g (30 % by weight) AMPS (2-acrylamide-2-methacrylic sulfonic acid), nitrogen protects heated and stirred and add 1.0gAIBN (Diisopropyl azodicarboxylate) to dissolution of solid, 70 ℃ of reactions were added 0.5gAIBN after 3 hours, react again after 4 hours and add dibutyl tin laurate 0.1g, 71.5gMOI (X2 example compound), ZJ-701(nitroxyl free radical piperidine alcohols) 0.1g, after 1 hour, reaction finishes.
Solid content is 34.1% weight, GPC weight-average molecular weight Mw=55200, iodine number Iv=43.1gI2/100g resin.
Embodiment 11(multipolymer K)
At 1000 ml band temperature control heatings, mechanical stirring, in the four-hole boiling flask of condensing reflux and nitrogen protection device, add the DMF (N that 500 g cross through anhydrous sodium sulfate drying, dinethylformamide) and 50.0g (25 % by weight) SM (vinylbenzene), 60.0g (30 % by weight) AN (vinyl cyanide), 80.0g (40 % by weight) HEMA (hydroxyethyl methylacrylate), 10.0g (5 % by weight) AMPS (2-acrylamide-2-methacrylic sulfonic acid), nitrogen protects heated and stirred and add 1.0gAIBN (Diisopropyl azodicarboxylate) to dissolution of solid, 70 ℃ of reactions were added 0.5gAIBN after 3 hours, react again after 4 hours and add dibutyl tin laurate 0.1g, 95.4gMOI (X2 example compound), ZJ-701(nitroxyl free radical piperidine alcohols) 0.1g, after 1 hour, reaction finishes.
Solid content is 37.1% weight, GPC weight-average molecular weight Mw=61700, iodine number Iv=52.8gI2/100g resin.
Synthetic comparative example multipolymer a, multipolymer c, multipolymer e.Multipolymer a and copolymer A, multipolymer d and multipolymer D compare, and multipolymer agent structure is identical, and difference is that multipolymer a, multipolymer c be not containing the two keys of active ammonia esterification; Multipolymer e and multipolymer E compare, and multipolymer agent structure is identical, and difference is that multipolymer e is not the two keys of grafting ammonia esterification activity, and grafting is the two keys of halo, and grafting method and technique are not identical yet.
(multipolymer a) for comparative example 1
At 1000 ml band temperature control heatings, mechanical stirring, in the four-hole boiling flask of condensing reflux and nitrogen protection device, add the DMF (N that 500 g cross through anhydrous sodium sulfate drying, dinethylformamide) and 120.0g (60 % by weight) SM (vinylbenzene), 40.0g (20 % by weight) AN (vinyl cyanide), 20.0g (10 % by weight) HEMA (hydroxyethyl methylacrylate), 20.0g (10 % by weight) AMPS (2-acrylamide-2-methacrylic sulfonic acid), nitrogen protects heated and stirred and add 1.0gAIBN (Diisopropyl azodicarboxylate) to dissolution of solid, 70 ℃ of reactions were added 0.5gAIBN after 3 hours, reacting reaction after 4 hours finishes again.
Solid content is 27.7% weight, GPC weight-average molecular weight Mw=55600.
Comparative example 2(multipolymer d)
At 1000 ml band temperature control heatings, mechanical stirring, in the four-hole boiling flask of condensing reflux and nitrogen protection device, add N,N-DIMETHYLACETAMIDE and 110.0g (55 % by weight) SM (vinylbenzene) that 500g crosses through anhydrous sodium sulfate drying, 30.0g (15 % by weight) MAN (cyanacrylate), 30.0g (15 % by weight) vinylformic acid-2-hydroxyl-3-phenoxy group propyl ester, 30.0g (15 % by weight) PEGMA (methoxy polyethylene glycol methacrylate-styrene polymer, Mn=2040), nitrogen protects heated and stirred and adds 1.0gAIBN (Diisopropyl azodicarboxylate) after evenly, 80 ℃ of reactions were added 0.5gAIBN after 3 hours, reacting reaction after 4 hours finishes again.
Solid content is 27.7% weight, GPC weight-average molecular weight Mw=70200.
Comparative example 3(multipolymer e)
At 1000 ml band temperature control heatings, mechanical stirring, in the four-hole boiling flask of condensing reflux and nitrogen protection device, add pimelinketone and 110.0g (55 % by weight) SM (vinylbenzene) that 500g crosses through anhydrous sodium sulfate drying, 30.0g (15 % by weight) AN (vinyl cyanide), 20.0g (10 % by weight) vinylformic acid, 40.0g (20 % by weight) ACMO (acrylamide morpholine), nitrogen protects heated and stirred and adds 1.0gAIBN (Diisopropyl azodicarboxylate) after evenly, 120 ℃ of reactions were added 0.5gAIBN after 3 hours, react again after 4 hours and add benzyl trimethyl ammonium chloride 0.48g, triphenylphosphine 0.3g, nitroxyl free radical piperidines 0.15g, 3-bromopropylene 28.1g, 90 ℃ are reacted 1.5 hours, 110 ℃ of reaction reaction end after 1.5 hours.
Solid content is 31.3% weight, GPC weight-average molecular weight Mw=62500, iodine number Iv=37.1gI2/100g resin.
Use above-mentioned water solubility copolymer, that makes that heat susceptible coating contains above-mentioned water solubility copolymer exempts from chemical treatment temperature-sensitive sensitive lithographic plate.
Version base is processed: the present invention's version base used is aluminium plate base through electrolyzing and coarsening and anodic oxidation and after carrying out sealing of hole processing, and its medullary ray average boldness is at 0. 2-0. 6 u m.Preferred 0. 3-0. 5 u m.Version base like this can make by the method for various electrolyzing and coarsening.Aluminium plate base of the present invention is high purity aluminium plate, and its aluminium content is preferably in more than 99%.Suitable aluminium plate base is (but lose, being 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 that contains organic solvent.Wherein, with the aqueous solution of hydrochloric acid, nitric acid or their salt, make electrolytic solution better.First aluminium plate is placed in the aqueous solution of sodium hydroxide, potassium hydroxide, sodium carbonate, water glass etc. of 1 %-30%, at the temperature of 20-80 ℃, carries out the 5-250 chemical corrosion of second.Then in the nitric acid of 10%-30% or sulfuric acid with the temperature neutralization of 20-70 ℃, to remove grey matter.Like this through the aluminium plate of clean, at the temperature of 10-6O ℃, the square wave changing with positive and negative interaction, bench-type ripple or sine wave etc., with the current density of 5-100A/d ㎡, electrolysis treatment 10-300 second in the electrolytic solution of nitric acid or hydrochloric acid.Then, the aluminium plate through electrolysis carries out anodic oxidation treatment.Sulfuric acid process is used in anodic oxidation conventionally.The concentration of the sulfuric acid using is 5-30%, and current density is 1-15A/d ㎡, and oxidizing temperature is at 20-60 ℃, and oxidization time is 5-250 second, to form the oxide film of 1-10 g/ ㎡.The oxide film forming like this has higher oxide film micropore conventionally, and adsorptive power is stronger, is easy to adhere to foul.So conventionally also need to carry out sealing of hole processing.Sealing of hole is processed and can be used various methods, take reach sealing oxide film micropore 50-80% volume as good.
The maximum absorption wavelength scope of the contained infrared absorbing compounds of heat susceptible coating is 780-1100nm, is selected from triarylamine dyestuff, thiazole dye, indoline dye, oxazole dyestuff, cyanine dyes, polyaniline dye, polypyrole dye, polythiophene dye, leuco dye and phthalocyanine pigment and dyestuff etc.
The contained radical-forming agent of heat susceptible coating comprises: salt, the triaizine compounds that contains trihalomethyl group, superoxide, azo polymerization starter, triazo-compound and quinone two nitrine, in them, the triaizine compounds of trihalomethyl group and salt become preferably because of its hypersensitivity.
The contained unsaturated monomer of heat susceptible coating comprises: Viscoat 295, trimethylolpropane tris (acryloyl-oxy propyl group) ether, trimethylolethane trimethacrylate acrylate, pentaerythritol triacrylate, pentaerythritol tetracrylate, six vinylformic acid dipentaerythritol ester, three vinylformic acid sorbitol esters, , three (acrylyl oxy-ethyl) isocyanic ester and polyester acrylic ester oligomer, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate methacrylic ester, Ethylene glycol dimethacrylate, dimethacrylate-1, 3-butanediol ester, dimethacrylate hexylene glycol ester, dimethacrylate pentaerythritol ester, trimethylammonium vinylformic acid pentaerythritol ester, pentaerythritol tetramethacrylate, dimethacrylate dipentaerythritol ester, and contain amino ester etc.These all esters all can be preferably with in the present invention.Monomer can be used with the form of its mixture.
The contained thermal polymerization inhibitor of heat susceptible coating comprises: quinhydrones, p methoxy phenol, ditertbutylparacresol, pyrogallol, tert-butyl catechol, benzoquinones, 4,4'-thiobis-(3 methy 6 tert butyl phenol), 2,2 '-methylene-bis (4-methyl isophthalic acid 6-tert.-butyl phenol), and uncle's cerium salt of N-nitroso-group phenyl oxyamine etc.
Preparation sensitization liquid solvent comprises: acetone, methyl ethyl ketone, hexanaphthene, ethyl acetate, ethylene dichloride, tetrahydrofuran (THF), toluene, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, glycol dimethyl ether, propylene glycol monomethyl ether, propylene-glycol ethyl ether, methyl ethyl diketone, pimelinketone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethyl cellosolve acetate, glycol isopropyl ether, butyl glycol ether acetic ester, 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 ester, N.N-dimethyl formamide, methyl-sulphoxide, methyl lactate and ethyl lactate etc.Solvent can be used with pure substance form or form of mixtures.The solid content of coating mixture is generally 2-50% (weight).
Photosensitive composition of the present invention conventionally with this field oneself know technology coating (as, cutter is coated with, blade coating, bar is coated with, roller coat, extrusion etc.) on version base.Photosensitive composition of the present invention is dissolved in to suitable solvent or/and in water, be made into coating fluid.
Make forme.
Sensitive lithographic plate 1(is containing copolymer A)
Version base hydrophilicity-imparting treatment: the aqueous solution of extrusion coated 1% water-soluble polymers A of the present invention on above-mentioned version base, then at 120 ℃, be dried 30 seconds, obtain the coating dry weight of 1.5g/ ㎡.
Each component of sensitization liquid 1(by weight)
Copolymer A 1.6 of the present invention
Polyurethane acroleic acid performed polymer 0.64
Polyfunctional group Acrylic Acid Monomer (Sartomer 399) 0.86
Infrared absorbing agents ADS830AT 0.03
2-(4-p-methoxy-phenyl)-4, two (the trichloromethyl)-s-triazine 0.03 of 6-
Nitroxyl free radical piperidine alcohols 0.03
BYK306 0.012
Alkaline bright blue 0.032
1-methoxy-2-propanol 32.80
The above-mentioned sensitization liquid of extrusion coated on above-mentioned version base is then dried 60 seconds at 120 ℃, obtains the coating dry weight of 1.8g/ ㎡.
The chemical treatment temperature-sensitive version of exempting from that contains water solubility copolymer of the present invention is negative aggretion type plate; in order to reduce the inhibition effect of oxygen to polymerization; on above-mentioned plate, coating, as lower protective layer, as the material for the protection of layer, preferably has the water-soluble polymers of higher crystallinity.Specifically there is water-soluble polymers, as the polyvinyl alcohol of partial hydrolysis, polyvinylpyrrolidone, acid cellulose derivative, gelatin, Sudan Gum-arabic etc.Protective layer is answered the fundamental propertys such as oxygen barrier and water development removeability for tool.
Each component of protective layer 1(by weight)
PVAC polyvinylalcohol-205(Japan Kuraray) 17
Polyvinylpyrrolidone PVPK30(Germany BASF) 3
Emulsifier op-10 (German Durham) 0.45
Deionized water 480
The above-mentioned protective layer of extrusion coated on above-mentioned plate is then dried 120 seconds at 120 ℃, obtains the coating dry weight of 2.0g/ ㎡.
The plate obtaining like this, on all-victorious 800 thermo-sensitive platemaking machines of Kodak, exposes with 160mj/c ㎡, and then on MASTER VIEW developing machine, the pure tap water of temperature with 40 ℃ rinses 30-50 second, is then printed on the machine, and also can directly be contained on printing press and print.Plate performance sees below table.
Sensitive lithographic plate 2(is containing multipolymer B)
Version base hydrophilicity-imparting treatment: the aqueous solution of extrusion coated 1% water-soluble polymers B of the present invention on above-mentioned version base, then at 120 ℃, be dried 30 seconds, obtain the coating dry weight of 1.5g/ ㎡.
Each component of sensitization liquid 2(by weight)
Multipolymer B 1.6 of the present invention
Polyurethane acroleic acid performed polymer 0.64
Polyfunctional group Acrylic Acid Monomer (Sartomer 399) 0.86
Infrared absorbing agents ADS830AT 0.03
2-(4-p-methoxy-phenyl)-4, two (the trichloromethyl)-s-triazine 0.03 of 6-
Nitroxyl free radical piperidine alcohols 0.03
BYK306 0.012
Alkaline bright blue 0.032
1-methoxy-2-propanol 32.80
The above-mentioned sensitization liquid of extrusion coated on above-mentioned version base is then dried 60 seconds at 120 ℃, obtains the coating dry weight of 1.8g/ ㎡.
On plate, be coated with protective layer formula and technique with forme 1, mask-making technology is also with sensitive lithographic plate 1.Plate performance sees below table.
Sensitive lithographic plate 3(is containing multipolymer C)
Version base hydrophilicity-imparting treatment: the aqueous solution of extrusion coated 1% water-soluble polymers C of the present invention on above-mentioned version base, then at 120 ℃, be dried 30 seconds, obtain the coating dry weight of 1.5g/ ㎡.
Each component of sensitization liquid 3(by weight)
Multipolymer C 1.6 of the present invention
Polyurethane acroleic acid performed polymer 0.64
Polyfunctional group Acrylic Acid Monomer (Sartomer 399) 0.86
Infrared absorbing agents ADS830AT 0.03
2-(4-p-methoxy-phenyl)-4, two (the trichloromethyl)-s-triazine 0.03 of 6-
Nitroxyl free radical piperidine alcohols 0.03
BYK306 0.012
Alkaline bright blue 0.032
1-methoxy-2-propanol 32.80
The above-mentioned sensitization liquid of extrusion coated on above-mentioned version base is then dried 60 seconds at 120 ℃, obtains the coating dry weight of 1.8g/ ㎡.
On plate, be coated with protective layer formula and technique with forme 1, mask-making technology is also with sensitive lithographic plate 1.Plate performance sees below table.
Sensitive lithographic plate 4(is containing multipolymer D)
Version base hydrophilicity-imparting treatment: the aqueous solution of extrusion coated 1% water-soluble polymers D of the present invention on above-mentioned version base, then at 120 ℃, be dried 30 seconds, obtain the coating dry weight of 1.5g/ ㎡.
Each component of sensitization liquid 4(by weight)
Multipolymer D 1.6 of the present invention
Polyurethane acroleic acid performed polymer 0.64
Polyfunctional group Acrylic Acid Monomer (Sartomer 399) 0.86
Infrared absorbing agents ADS830AT 0.03
2-(4-p-methoxy-phenyl)-4, two (the trichloromethyl)-s-triazine 0.03 of 6-
Nitroxyl free radical piperidine alcohols 0.03
BYK306 0.012
Alkaline bright blue 0.032
1-methoxy-2-propanol 32.80
The above-mentioned sensitization liquid of extrusion coated on above-mentioned version base is then dried 60 seconds at 120 ℃, obtains the coating dry weight of 1.8g/ ㎡.
On plate, be coated with protective layer formula and technique with forme 1, mask-making technology is also with sensitive lithographic plate 1.Plate performance sees below table.
Sensitive lithographic plate 5(is containing multipolymer E)
Version base hydrophilicity-imparting treatment: the aqueous solution of extrusion coated 1% water-soluble polymers E of the present invention on above-mentioned version base, then at 120 ℃, be dried 30 seconds, obtain the coating dry weight of 1.5g/ ㎡.
Each component of sensitization liquid 5(by weight)
Multipolymer E 1.6 of the present invention
Polyurethane acroleic acid performed polymer 0.64
Polyfunctional group Acrylic Acid Monomer (Sartomer 399) 0.86
Infrared absorbing agents ADS830AT 0.03
2-(4-p-methoxy-phenyl)-4, two (the trichloromethyl)-s-triazine 0.03 of 6-
Nitroxyl free radical piperidine alcohols 0.03
BYK306 0.012
Alkaline bright blue 0.032
1-methoxy-2-propanol 32.80
The above-mentioned sensitization liquid of extrusion coated on above-mentioned version base is then dried 60 seconds at 120 ℃, obtains the coating dry weight of 1.8g/ ㎡.
On plate, be coated with protective layer formula and technique with forme 1, mask-making technology is also with sensitive lithographic plate 1.Plate performance sees below table.
Adopt above-mentioned same method to prepare sensitive lithographic plate 6 ~ 11(respectively containing multipolymer F ~ K).
Sensitive lithographic plate 12(containing multipolymer a)
Version base hydrophilicity-imparting treatment: the aqueous solution of extrusion coated 1% water-soluble polymers a on above-mentioned version base, then at 120 ℃, be dried 30 seconds, obtain the coating dry weight of 1.5g/ ㎡.
Each component of sensitization liquid 6(by weight)
Water solubility copolymer a 1.6
Polyurethane acroleic acid performed polymer 0.64
Polyfunctional group Acrylic Acid Monomer (Sartomer 399) 0.86
Infrared absorbing agents ADS830AT 0.03
2-(4-p-methoxy-phenyl)-4, two (the trichloromethyl)-s-triazine 0.03 of 6-
Nitroxyl free radical piperidine alcohols 0.03
BYK306 0.012
Alkaline bright blue 0.032
1-methoxy-2-propanol 32.80
The above-mentioned sensitization liquid of extrusion coated on above-mentioned version base is then dried 60 seconds at 120 ℃, obtains the coating dry weight of 1.8g/ ㎡.
On plate, be coated with protective layer formula and technique with forme 1, mask-making technology is also with sensitive lithographic plate 1.Plate performance sees below table.
Sensitive lithographic plate 13(is containing multipolymer d)
Version base hydrophilicity-imparting treatment: the aqueous solution of extrusion coated 1% water-soluble polymers A of the present invention on above-mentioned version base, then at 120 ℃, be dried 30 seconds, obtain the coating dry weight of 1.5g/ ㎡.
Each component of sensitization liquid 7(by weight)
Water miscible multipolymer c 1.6
Polyurethane acroleic acid performed polymer 0.64
Polyfunctional group Acrylic Acid Monomer (Sartomer 399) 0.86
Infrared absorbing agents ADS830AT 0.03
2-(4-p-methoxy-phenyl)-4, two (the trichloromethyl)-s-triazine 0.03 of 6-
Nitroxyl free radical piperidine alcohols 0.03
BYK306 0.012
Alkaline bright blue 0.032
1-methoxy-2-propanol 32.80
The above-mentioned sensitization liquid of extrusion coated on above-mentioned version base is then dried 60 seconds at 120 ℃, obtains the coating dry weight of 1.8g/ ㎡.
On plate, be coated with protective layer formula and technique with forme 1, mask-making technology is also with sensitive lithographic plate 1.Plate performance sees below table.
Sensitive lithographic plate 14(is containing multipolymer e)
Version base hydrophilicity-imparting treatment: the aqueous solution of extrusion coated 1% water-soluble polymers e of the present invention on above-mentioned version base, then at 120 ℃, be dried 30 seconds, obtain the coating dry weight of 1.5g/ ㎡.
Each component of sensitization liquid 8(by weight)
Water solubility copolymer e 1.6
Polyurethane acroleic acid performed polymer 0.64
Polyfunctional group Acrylic Acid Monomer (Sartomer 399) 0.86
Infrared absorbing agents ADS830AT 0.03
2-(4-p-methoxy-phenyl)-4, two (the trichloromethyl)-s-triazine 0.03 of 6-
Nitroxyl free radical piperidine alcohols 0.03
BYK306 0.012
Alkaline bright blue 0.032
1-methoxy-2-propanol 32.80
The above-mentioned sensitization liquid of extrusion coated on above-mentioned version base is then dried 60 seconds at 120 ℃, obtains the coating dry weight of 1.8g/ ㎡.
On plate, be coated with protective layer formula and technique with forme 1, mask-making technology is also with sensitive lithographic plate 1.Plate performance sees below table.
Application result by rear table shows, what contain the unsaturated water soluble vinyl multiple copolymer of ammonia esterification of the present invention exempts from chemical treatment temperature-sensitive sensitive lithographic plate, due to the ammonia ester bond existence of strong polarity, sensitive lithographic plate has strong adhesion, coating is tough and tensile, site netting twine is Well-recovered, it is dirty not go up, water development easy, pressrun advantages of higher; And the performances such as sticking power, site netting twine reductibility, water development and pressrun of the forme coating that does not contain the two key multipolymers of ammonia esterification activity or contain halo activity double key multipolymer are all poor.
Table 1 embodiment and comparative example plate performance
Claims (7)
1. the unsaturated water soluble vinyl multiple copolymer of ammonia esterification, is characterized in that: it is the vinyl multiple copolymer that contains following structural unit:
-A-B-C(-X)-D-
A represents styrol structural unit;
B representative (methyl) acrylonitrile unit unit;
C representative is containing the vinyl copolymerization units of branched hydroxy group;
D representative is containing the vinyl copolymerization units of side chain hydrophilic group;
X represents the unsaturated monoisocyanates structural unit of C unit branched hydroxy group grafting;
The weight-average molecular weight of multipolymer is 5000-200000; Glass transition temperature is 30-260 ℃; The weight percent content of styrene copolymerized unit A in grafting multiple copolymer is not 30-80%; The weight percent content of (methyl) acrylonitrile compolymer unit B in grafting multiple copolymer is not 0.5%-40%; Containing the vinyl copolymerization units C of branched hydroxy group, at the weight percent content in grafting multiple copolymer not, be 0.5%-40%; Containing the vinyl copolymerization units D of side chain hydrophilic radical, at the weight percent content in grafting multiple copolymer not, be 0.5%-40%;
The structural formula of the unsaturated monoisocyanates structural unit X of described C unit branched hydroxy group grafting is:
In formula, R
1for hydrogen atom or methyl, R
2for ester group, penylene base or valence link, the integer that r is 1-3; The molar ratio of unsaturated monoisocyanates X and vinyl copolymerization units C institute hydroxyl is 0.1-1.0;
Containing hydrophilic radical in the vinyl copolymerization units D of side chain hydrophilic radical, be at least one of carboxyl, amide group, sulfonic group, phosphate or ether;
Described X structural unit is
In any one.
2. the unsaturated water soluble vinyl multiple copolymer of ammonia esterification according to claim 1, is characterized in that: the weight-average molecular weight of multipolymer is 15000-100000; Glass transition temperature is 40-150 ℃; The weight percent content of styrene copolymerized unit A in grafting multiple copolymer is not 40-70%; The weight percent content of (methyl) acrylonitrile compolymer unit B in grafting multiple copolymer is not 5%-30%; Containing the vinyl copolymerization units C of branched hydroxy group, at the weight percent content in grafting multiple copolymer not, be 5-30%; Containing the vinyl copolymerization units D of side chain hydrophilic radical, at the weight percent content in grafting multiple copolymer not, be 5-30%.
3. the unsaturated water soluble vinyl multiple copolymer of ammonia esterification according to claim 2, is characterized in that: the weight-average molecular weight of multipolymer is 40000-80000; Glass transition temperature is 60-130 ℃; The weight percent content of styrene copolymerized unit A in grafting multiple copolymer is not 50-60%; The weight percent content of (methyl) acrylonitrile compolymer unit B in grafting multiple copolymer is not 10-20%; Containing the vinyl copolymerization units C of branched hydroxy group, at the weight percent content in grafting multiple copolymer not, be 10-20%; Containing the vinyl copolymerization units D of side chain hydrophilic radical, at the weight percent content in grafting multiple copolymer not, be 10-20%.
4. the unsaturated water soluble vinyl multiple copolymer of ammonia esterification according to claim 1, is characterized in that: the molar ratio of the unsaturated monoisocyanates X of C unit branched hydroxy group grafting and vinyl copolymerization units C institute hydroxyl is 0.5-1.00.
5. the synthetic method of the unsaturated water soluble vinyl multiple copolymer of ammonia esterification claimed in claim 1, it is characterized in that: first carry out synthesize-A-B-C-D-multiple copolymer of multi-component copolymer reaction, then by C unit branched hydroxy group and unsaturated monoisocyanates X ammonia esterification grafting unsaturated double-bond.
6. the synthetic method of the unsaturated water soluble vinyl multiple copolymer of ammonia esterification according to claim 5, is characterized in that: reaction solvent adopts any one in ammonia ester level dimethyl formamide, N,N-DIMETHYLACETAMIDE or methylethylketone.
7. the synthetic method of the unsaturated water soluble vinyl multiple copolymer of ammonia esterification according to claim 5, it is characterized in that: the catalyzer of described ammonia graft esterification reaction is lead octoate 36, stannous octoate, dibutyl tin laurate, triethylenediamine, cobalt octoate or iron octoate, consumption is the 0.005-10% of unsaturated monoisocyanates monomer weight of feeding intake; Graft reaction temperature is 40-120 ℃; Stopper is a kind of in Resorcinol, para benzoquinone, toluhydroquinone, MEHQ, 2-Tert. Butyl Hydroquinone, 2,5 di tert butyl hydroquinone, nitroxyl free radical piperidine alcohols.
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