CN102504073B - Urethanation modified hybrid phenolic resin and preparation method thereof - Google Patents
Urethanation modified hybrid phenolic resin and preparation method thereof Download PDFInfo
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- CN102504073B CN102504073B CN201110355430.1A CN201110355430A CN102504073B CN 102504073 B CN102504073 B CN 102504073B CN 201110355430 A CN201110355430 A CN 201110355430A CN 102504073 B CN102504073 B CN 102504073B
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Abstract
Urethanation modified hybrid phenolic resin is prepared through the following steps: the grafting of linear phenolic resin and ethylene monoisocyanates is conducted through the phenol hydroxyl urethanation reaction, then the linear phenolic resin serves as a high-polymer monomer to conduct the second radical linear polymerization independently or jointly with other ethylene monomers to obtain the hybrid phenolic resin; the weight-average molecular weight of the urethanation modified hybrid phenolic resin is 7.500 to 150.000; and the temperature of the softening point is 80 to 220 DEG C. The urethanation modified hybrid phenolic resin is used for thermosensitive flat printing plates, and can obviously enhance the solvent resistance and the durability of the thermal plate due to the existence of strongly polar urethane links, and the flat printing plate has the advantages of strong coating adhesion and toughness.
Description
Technical field
The invention belongs to printing technology, be specifically related to a kind of thermal CTP plate material ammonia esterification modification hybrid phenol-formaldehyde resin and preparation 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 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, the solvent resistance and the Nai Yin ability that particularly improve plate are the focuses that thermal CTP plate material is developed.
Plate solvent resistant refers to the corrosion of the organic solvent in the resistance to various printing chemical of printing plate, as use in printing washing oil, fountain solution, gum-solution, forme preserving agent, plate cleaners, ink particularly UV ink-washing oil corrosion.
Plate wear resistance and solvent resistance have certain cognation, but not absolute.In general, the good plate of solvent resistance generally has higher wear resistance, but the good plate of wear resistance not necessarily solvent resistance is all right, the particularly erosion of the plate ink of resistance to UV.
The method improving the solvent resistance of heat-sensitive CTP plate plate and Nai Yin ability is a lot, wherein one of most important method is exactly the exploitation of printing plate organism particularly functional film-forming resin, such as Kodak patent CN101321632A is disclosed introduces phosphoric acid or diamantane side base at polymkeric substance, improves the chemical-resistant of plate.
Resol is a kind of important temperature-sensitive version film-forming resin, can be improved solvent resistance and the pressrun of temperature-sensitive version by the modification of resol, modification.
The modification of printing plate caustic solubility resol, modification are generally carry out modification by the distant pawl group of phenolic hydroxyl group, such as resol phenolic hydroxyl group disclosed in EP-A 0934822 and sulfonic group or carboxy moiety esterification modification.
Agfa Corp. EP [31] 02102446.8, CN1688441A discloses a kind of method of modifying by phenolic hydroxyl group distant pawl group, resol being carried out to diazonium salt grafting, is used for improving the chemical resistance of temperature-sensitive version.Method disclosed in Ai Kefa carries out diazonium salt graft modification to resol, forms azo-aromatic yl group (-N=N-Q group, Q is aromatic group), improves chemical resistance of coating.
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.
Kodak proposes at WO2004/033206, introduces barbituric acid group in macromolecule resin side chain, obviously can improve solvent resistance and the wear resistance of plate coating.Kodak discloses a kind of method of the phenolic hydroxyl group grafting barbituric acid group by resol.
Kodak discloses a kind of QHB modified phenolic resins in WO2004/033206, CN200380104739.7.QHB modified phenolic resins is with iso-cytosine (2-amino-4-hydroxy pyrimidine) and isocyanate-modified resol, forms strong polarity tetrahydrochysene bonding structure, is used in multilayer heat-sensitive version upper strata i.e. the second polymeric layer, to improve the wear resistance of plate.
Fujiphoto JP 2000-7-13 2000-213142, CN01120259 describe a kind of Lighographic printing plate precursor, comprise the polymkeric substance of hydrophilic grafts chain containing three-dimensional polyisocyanates precrosslink structure, three-dimensional polyisocyanates precrosslink structure improves the pressrun of printing plate.
The modification of above-mentioned resol, partially enclosed due to phenolic hydroxyl group, the caustic solubility of resin and plate more or less will arrive influenced.
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 by partially enclosed due to phenolic hydroxyl group that phenolic resin modified method improves that plate solvent resistant ability and Nai Yin ability exist, the caustic solubility of resin and plate will arrive affected shortcoming.There is provided a kind of brand-new ammonia esterification modification hybrid phenol-formaldehyde resin and preparation method thereof, modified resol is used for heat-sensitive CTP plate and has good film-forming property, solvent resistant, advantage that pressrun is high, and the caustic solubility of plate is unaffected.
For achieving the above object, the present invention adopts following technical scheme:
Ammonia esterification modification hybrid phenol-formaldehyde resin of the present invention, it is by phenolic hydroxyl group ammonia esterification grafting vinyl monoisocyanates by linear phenolic resin, then as high polymer monomer separately or and other vinyl monomer carry out the hybrid phenol-formaldehyde resin that second time free radical linear polymerization obtains, ammonia esterification modification hybrid phenol-formaldehyde resin weight-average molecular weight is 7500-150000; Softening temperature is 80-220 DEG C.
Described linear phenolic resin is phenol, p-cresol, meta-cresol and composition thereof and the linear condensation product of formaldehyde, and molecular weight is 2500-14000.
Described vinyl monoisocyanates has following general structure:
In formula, R
1for hydrogen atom or methyl, R
2for ester group, penylene base or carbon-carbon single bond, r is the integer of 1-3, and phenolic hydroxyl group ammonia graft esterification rate is 10-90%.
Other described vinyl monomer is contain at least one in the vinyl monomer of sulfoamido or reactive maleimide and N-replacement caustic solubility derivative thereof in structure, and its weight accounts for the 10-50% of copolymerization weight.
The preparation method of ammonia esterification modification hybrid phenol-formaldehyde resin of the present invention, by linear phenolic resin in reaction solvent, under nitrogen protection condition, heated and stirred adds catalyzer after linear phenolic resin dissolves, then vinyl monoisocyanates is dripped, react to ammonia esterification terminal at 40-120 DEG C, unsaturated monoisocyanates and phenolic hydroxyl group molar ratio are 0.05-0.95, and catalyst levels is the 0.005-10% of unsaturated monoisocyanates monomer weight; Then as high polymer monomer separately or and other vinyl monomer carry out the hybrid phenol-formaldehyde resin that second time free radical linear polymerization obtains.
Below the present invention is elaborated:
1, by ammonia esterification, in resol, introduce strong polarity ammonia ester bond, introduce double bond simultaneously;
2, then by the independent homopolymerization of resol free radical containing double bond of ammonia esterification or and other are containing extraordinary monomer copolymerizations of caustic solubility group, form ammonia esterification modification hybrid phenol-formaldehyde resin;
3, introduce containing the molten group of alkali and special wear-resisting solvent resistant group during copolymerization.
Strengthen molecular resin amount owing to introducing strong polarity ammonia ester bond, special wear-resisting solvent resistant group and repolymerization hydridization in resin, the solvent resistant of plate, pressrun obtained and significantly improved.Meanwhile, second time free-radical polymerized introduce in the structure the molten group of alkali improve resol graft modification in the past after phenolic hydroxyl group reduce or cause greatly the affected shortcoming of plate caustic solubility because of molecule quantitative change.
Synthetic route is in two steps:
1, first phenolic hydroxyl group ammonia esterification grafting vinyl monoisocyanates is passed through by linear phenolic resin;
2, by the resol after grafting vinyl monoisocyanates, second time free radical linear polymerization is carried out separately or with other extraordinary monomer containing caustic solubility group as high polymer monomer.
It is below detailed description of the present invention.
The present invention discloses a kind of ammonia esterification modification hybrid phenol-formaldehyde resin and preparation method thereof, it is by linear phenolic resin by phenolic hydroxyl group ammonia esterification grafting vinyl monoisocyanates, then as high polymer monomer separately or and other vinyl monomer carry out that second time free radical linear polymerization obtains.
Linear phenolic resin of the present invention is the linear product that phenols and aldehydes carry out condensation reaction and obtain.
Specifiable phenols example have phenol, m-cresol, p-cresol ,/to mixed methyl phenol, pyrogallol, isopropyl-phenol, tert.-butyl phenol, tert.-amyl phenol, hexylphenol, cyclohexylphenol, the chloro-uncle's 6-butylphenol of 3-methyl-4-and phenolic group derivative as hydroxy styrenes etc.
Specifiable aldehydes example alkanoic has formaldehyde, acetaldehyde, propenal, crotonaldehyde and aromatic series, heterocycle race aldehyde etc.
Linear phenolic resin of the present invention preferentially selects the condensation product by P-F, hydroxy styrenes-formaldehyde or mixed phenol (phenol ,/to mixed methyl phenol)-formaldehyde, more preferably the linear condensation product of phenol, p-cresol, meta-cresol and composition thereof and formaldehyde.
Linear phenolic resin of the present invention preferentially selects the linear condensation product of phenol, p-cresol, meta-cresol and composition thereof and formaldehyde, and synthesis technique can see " newly testing chemistry " polymer chemistry section the 300th (1993, Japanese Wan Shan press).
Synthesize the preferred 1000-100000 of linear phenolic resin weight-average molecular weight of the present invention, be more preferably 2000-50000, most preferably be as 2500-14000.
The companies such as commercial linear phenolic resin can become from sky, Weihai, Switzerland DKSH, Bakelite, Clariant GmbH, B.P. chemistry buy.
Unsaturated monoisocyanates (code name M) structural formula synthesizing ammonia esterification modification hybrid phenol-formaldehyde resin of the present invention grafting used is:
R
1for hydrogen atom or methyl, R
2for ester group, penylene base or carbon-carbon single bond etc., r is the integer of 1-3.
Detailed example is shown in following structural formula, but the present invention is not limited to the structural formula of following M1-M3.
M1
M2
M3
The reaction of synthesis Inventive polymers ammonia graft esterification, unsaturated monoisocyanates and the preferred 0.05-0.95 of phenolic hydroxyl group molar ratio, optimum is 0.1-0.9, or phenolic hydroxyl group ammonia graft esterification rate is preferred 5-95%, and optimum is
10-90%。
The reaction solvent of the unsaturated monoisocyanates of grafting must be not containing the solvent of active proton hydrogen, as Isosorbide-5-Nitrae-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.
The catalyzer of the unsaturated monoisocyanates of grafting is as lead octoate 36, stannous octoate, dibutyl tin laurate, triethylenediamine, cobalt octoate, iron octoate etc., preferably dibutyl tin laurate, 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 DEG C, preferably at 60-110 DEG C.
Ammonia esterification completes the judgement of terminal: ammonia esterification completes the mark of terminal: disappeared by peak, infrared spectra detection of active isocyanate group 2275 place, or liquid phase gel chromatography detection of active isocyanate group disappears, also can disappear by Di-n-Butyl Amine reverse volumetry detection of active isocyanate group.
Resol after ammonia esterification, the activity double key due to grafting, also directly can be used as photosensitive resin and the film-forming resin of polymerizability negativity plate.
The present invention is by further for the resol after ammonia esterification hydridization.
Linear phenolic resin is by after phenolic hydroxyl group ammonia esterification grafting vinyl monoisocyanates, can be used as the independent homopolymerization of high polymer monomer or carry out the linear copolymerization of second time free radical with other vinyl monomer, polymerization obtains ammonia esterification modification hybrid phenol-formaldehyde resin of the present invention.
Homopolymerization: the resol after ammonia graft esterification is as the independent homopolymerization of high polymer monomer, and the hybrid phenol-formaldehyde resin obtained is as temperature-sensitive version film-forming resin, and the molten group of its alkali is still phenolic hydroxyl group.Because the reaction of ammonia graft esterification will consume part phenolic hydroxyl group, the alkali capacitive of the hybrid phenol-formaldehyde resin that after polymerization obtains certainly will be affected, so, ammonia graft esterification rate can not be too high, resol before grafting selects hydroxyl value larger as far as possible, the resol that caustic solubility is good, in order to avoid the caustic solubility affecting hybrid resin.
Copolymerization: the resol after ammonia graft esterification can carry out the linear copolymerization of second time free radical by other vinyl monomer as high polymer monomer.
Other vinyl monomer can select the monomer of any free redical copolymerization in theory, as containing following monomer and derivative vinyl monomer: the known monomer of (methyl) acrylic acid or the like, (methyl) esters of acrylic acid, (methyl) acrylic amide, vinyl ester, styrenic, vinyl cyanide, maleic anhydride class, maleimide, lactone etc.
As the monomer that the present invention preferentially selects, the molten group of alkali should be possessed, the molten group of side base alkali can be formed in hybrid resin after copolymerization hydridization, the caustic solubility due to the loss of ammonia graft esterification reaction consumption part phenolic hydroxyl group can be made up, after polymerization resol molecular weight can be made up simultaneously and increase the caustic solubility impact brought.
Possess the vinyl monomer of caustic solubility group, specifiable as the vinyl monomer containing the groups such as carboxyl, phenolic hydroxyl group, sulfonic group, phosphate, sulfoamido, active imide base and the molten derivative of alkali thereof.
As the monomer that the present invention preferentially selects, the above-mentioned vinyl monomer possessing caustic solubility group also can be preferred further.In order to increase solvent resistance and the wear resistance of hybrid resin, can the preferably comparatively large or chemicals-resistant corrosion of polarity or the good known special engineering plastics polymerization single polymerization monomer of wear resistance, possess in above-mentioned monomer simultaneously this characteristic monomer we preferably replace the vinyl monomer of caustic solubility derivative containing sulfoamido or reactive maleimide and N-thereof, wherein the N-substituting group of maleimide must have caustic solubility.
The vinyl monomer of caustic solubility derivative is replaced containing sulfoamido or reactive maleimide and N-thereof, specifiable have N-(4-sulfoamido benzene) Methacrylamide, N-(4-ethyl sulfonamide base benzene) Methacrylamide, N-(4-benzenesulfonyl amine phenyl) Methacrylamide, N-(4-carboxyl benzene) Methacrylamide maleimide, N-(4-hydroxybenzene) maleimide, N-(4-sulfoamido benzene) maleimide, N-(4-ethyl sulfonamide base benzene) maleimide, N-(4-benzenesulfonyl amine phenyl) maleimide, N-(4-carboxyl benzene) maleimide etc.
The optional random copolymerization of copolyreaction or block copolymerization, preferred random copolymerization.The initiator of radical polymerization comprises superoxide 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.
Whole ammonia esterification hybrid modification reaction can adopt single stage method or two-step approach to complete, preferably adopt one-step synthesis method, adopt single stage method, but reaction solvent must be recited above not containing 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 DEG C, preferably at 50-100 DEG C.
Second time free-radical polymerized polymerization degree n ' control be the key affecting resin property, molecular resin amount can be measured by gel permeation chromatography GPC, estimation second time co-polymeric degree n ' ≈ Mw (modified)/Mw (no-modified), wherein Mw (modified) is modified resol weight-average molecular weight, Mw (no-modified), for modified resol weight-average molecular weight is to control Raolical polymerizable condition, adjusts resin property.
The weight-average molecular weight of ammonia esterification modification hybrid phenol-formaldehyde resin of the present invention is 4000-300000, is preferably 6000-200000, most preferably is 7500-150000.Glass transition temperature is 30-300 DEG C, is preferably 50-250 DEG C, most preferably is 80-220 DEG C.
Ammonia esterification modification hybrid phenol-formaldehyde resin of the present invention, its purposes manufactures positive thermosensitive CTP version.
Temperature-sensitive sensitive lithographic plate is used for containing ammonia esterification modification hybrid phenol-formaldehyde resin of the present invention, obviously can strengthen solvent resistant performance and the pressrun of temperature-sensitive version, this is because the ammonia ester bond of strong polarity exists in ammonia esterification modification hybrid phenol-formaldehyde resin, sensitive lithographic plate has strong, the tough and tensile advantage of coating adhesion; Again because second time linear polymerization hydridization, in resol, introduce the unique construction unit containing the molten group of alkali, improve resistance to dissolubility and the wear resistance of resin, the caustic solubility of resol is unaffected simultaneously.
Embodiment
Here is synthesis example of the present invention, but the present invention is not limited to following example.
Ammonia esterification hybrid modification is carried out to resol 12 sample P 01-P12, obtains corresponding modified product P01M-P12M respectively.
Resol P01-P12: all purchased from Switzerland DKSH.Comonomer is all competing purchased from Shanghai thing.
Unsaturated monoisocyanates M1-M3, buys from Japanese Showa Denko K. K (SDK), M2 commercial disignation MOI.
Embodiment 1(resol P01, modified phenolic resins P01M)
Temperature control heating is with at 1000 ml, mechanical stirring, DMAC (the N that 565.7 g cross through anhydrous sodium sulfate drying is added in the four-hole boiling flask of condensing reflux and nitrogen protection device, N-N,N-DIMETHYLACETAMIDE) and 200.0g resol P01 (commercial product code: MV4020G, m/p=60/40, Mw ≈ 14000), nitrogen adds 1.0g dibutyl tin laurate after protecting 60 DEG C of heated and stirred to dissolution of solid, then 26.3gMOI(methylacryoyloxyethyl isocyanic ester is slowly instilled), react 4 hours, until disappeared by peak, infrared spectra detection of active isocyanate group 2275 place.
1.2gAIBN (Diisopropyl azodicarboxylate) is added, 70 DEG C of reaction reaction end after 23 hours in above-mentioned reaction solution.Reactant is separated out in deionized water, washs, 40 DEG C of vacuum-dryings, obtain homopolymerization modified phenolic resins P01M.Performance sees below table.
Embodiment 2(resol P02, modified phenolic resins P02M)
Temperature control heating is with at 1500 ml, mechanical stirring, DMAC (the N that 1091 g cross through anhydrous sodium sulfate drying is added in the four-hole boiling flask of condensing reflux and nitrogen protection device, N-N,N-DIMETHYLACETAMIDE) and 200.0g resol P02 (commercial product code: EPR6040A, m/p=40/60, Mw ≈ 2500), nitrogen adds 1.0g dibutyl tin laurate after protecting 60 DEG C of heated and stirred to dissolution of solid, then 236.4gMOI(methylacryoyloxyethyl isocyanic ester is slowly instilled), react 4 hours, until disappeared by peak, infrared spectra detection of active isocyanate group 2275 place.
2.2gAIBN (Diisopropyl azodicarboxylate) is added, 70 DEG C of reaction reaction end after 23 hours in above-mentioned reaction solution.Reactant is separated out in deionized water, washs, 40 DEG C of vacuum-dryings, obtain homopolymerization modified phenolic resins P02M.Performance sees below table.
Embodiment 3(resol P03, modified phenolic resins P03M)
Temperature control heating is with at 1000 ml, mechanical stirring, DMAC (the N that 598.5 g cross through anhydrous sodium sulfate drying is added in the four-hole boiling flask of condensing reflux and nitrogen protection device, N-N,N-DIMETHYLACETAMIDE) and 200.0g resol P03 (commercial product code: TR4020G, m/p=60/40, Mw ≈ 13000), nitrogen adds 1.0g dibutyl tin laurate after protecting 60 DEG C of heated and stirred to dissolution of solid, then 39.4gMOI(methylacryoyloxyethyl isocyanic ester is slowly instilled), react 4 hours, until disappeared by peak, infrared spectra detection of active isocyanate group 2275 place.
26.6g MI(maleimide is added in above-mentioned reaction solution), the DMAC that 66.5 g are dried, 1.3gAIBN (Diisopropyl azodicarboxylate), 70 DEG C of reaction reaction end after 23 hours.Reactant is separated out in deionized water, washs, 40 DEG C of vacuum-dryings, obtain modification by copolymerization resol P03M.Performance sees below table.
Embodiment 4(resol P04, modified phenolic resins P04M)
Temperature control heating is with at 3000 ml, mechanical stirring, DMAC (the N that 1058.3 g cross through anhydrous sodium sulfate drying is added in the four-hole boiling flask of condensing reflux and nitrogen protection device, N-N,N-DIMETHYLACETAMIDE) and 200.0g resol P04 (commercial product code: EPR5000B, mC/pC=50/50, Mw ≈ 3000), nitrogen adds 1.0g dibutyl tin laurate after protecting 60 DEG C of heated and stirred to dissolution of solid, then 223.3gMOI(methylacryoyloxyethyl isocyanic ester is slowly instilled), react 4 hours, until disappeared by peak, infrared spectra detection of active isocyanate group 2275 place.
423.3g MI(maleimide is added in above-mentioned reaction solution), the DMAC that 1058.3 g are dried, 4.2gAIBN (Diisopropyl azodicarboxylate), 70 DEG C of reaction reaction end after 23 hours.Reactant is separated out in deionized water, washs, 40 DEG C of vacuum-dryings, obtain modification by copolymerization resol P04M.Performance sees below table.
Embodiment 5(resol P05, modified phenolic resins P05M)
Temperature control heating is with at 2000 ml, mechanical stirring, DMAC (the N that 697g crosses through anhydrous sodium sulfate drying is added in the four-hole boiling flask of condensing reflux and nitrogen protection device, N-N,N-DIMETHYLACETAMIDE) and 200.0g resol P05 (commercial product code: PP3525G, p/phenol=35/65, Mw ≈ 11500), nitrogen adds 1.0g dibutyl tin laurate after protecting 60 DEG C of heated and stirred to dissolution of solid, then 78.8gMOI(methylacryoyloxyethyl isocyanic ester is slowly instilled), react 4 hours, until disappeared by peak, infrared spectra detection of active isocyanate group 2275 place.
49.2g N-4ASAM [chemical name: N-4 (sulfoamido phenyl) acrylamide] is added, the DMAC that 123 g are dried, 1.7gAIBN (Diisopropyl azodicarboxylate), 70 DEG C of reaction reaction end after 23 hours in above-mentioned reaction solution.Reactant is separated out in deionized water, washs, 40 DEG C of vacuum-dryings, obtain modification by copolymerization resol P05M.Performance sees below table.
Embodiment 6(resol P06, modified phenolic resins P06M)
Temperature control heating is with at 3000 ml, mechanical stirring, DMAC (the N that 958.3g crosses through anhydrous sodium sulfate drying is added in the four-hole boiling flask of condensing reflux and nitrogen protection device, N-N,N-DIMETHYLACETAMIDE) and 200.0g resol P06 (commercial product code: MV6020G, m/p=40/60, Mw ≈ 3800), nitrogen adds 1.0g dibutyl tin laurate after protecting 60 DEG C of heated and stirred to dissolution of solid, then 183.9gMOI(methylacryoyloxyethyl isocyanic ester is slowly instilled), react 4 hours, until disappeared by peak, infrared spectra detection of active isocyanate group 2275 place.
206.7g N-4ASAM [chemical name: N-4 (sulfoamido phenyl) acrylamide] is added, the DMAC that 516.8 g are dried, 3gAIBN (Diisopropyl azodicarboxylate), 70 DEG C of reaction reaction end after 23 hours in above-mentioned reaction solution.Reactant is separated out in deionized water, washs, 40 DEG C of vacuum-dryings, obtain modification by copolymerization resol P06M.Performance sees below table.
Embodiment 7(resol P07, modified phenolic resins P07M)
Temperature control heating is with at 2000 ml, mechanical stirring, DMAC (the N that 631.3 g cross through anhydrous sodium sulfate drying is added in the four-hole boiling flask of condensing reflux and nitrogen protection device, N-N,N-DIMETHYLACETAMIDE) and 200.0g resol P07 (commercial product code: EPR5010G, m/p=50/50, Mw ≈ 11000), nitrogen adds 1.0g dibutyl tin laurate after protecting 60 DEG C of heated and stirred to dissolution of solid, then 52.5gMOI(methylacryoyloxyethyl isocyanic ester is slowly instilled), react 4 hours, until disappeared by peak, infrared spectra detection of active isocyanate group 2275 place.
63.1g N-4HPAM [chemical name: N-4 (hydroxy phenyl) acrylamide] is added, the DMAC that 157.8g is dried, 1.6gAIBN (Diisopropyl azodicarboxylate), 70 DEG C of reaction reaction end after 23 hours in above-mentioned reaction solution.Reactant is separated out in deionized water, washs, 40 DEG C of vacuum-dryings, obtain modification by copolymerization resol P07M.Performance sees below table.
Embodiment 8(resol P08, modified phenolic resins P08M)
Temperature control heating is with at 3000 ml, mechanical stirring, DMAC (the N that 1025.5 g cross through anhydrous sodium sulfate drying is added in the four-hole boiling flask of condensing reflux and nitrogen protection device, N-N,N-DIMETHYLACETAMIDE) and 200.0g resol P08 (commercial product code: EPR6050G, m/p=40/60, Mw ≈ 4000), nitrogen adds 1.0g dibutyl tin laurate after protecting 60 DEG C of heated and stirred to dissolution of solid, then 210.2gMOI(methylacryoyloxyethyl isocyanic ester is slowly instilled), react 4 hours, until disappeared by peak, infrared spectra detection of active isocyanate group 2275 place.
273.5g N-4HPAM [chemical name: N-4 (hydroxy phenyl) acrylamide] is added, the DMAC that 683.8 g are dried, 3.4gAIBN (Diisopropyl azodicarboxylate), 70 DEG C of reaction reaction end after 23 hours in above-mentioned reaction solution.Reactant is separated out in deionized water, washs, 40 DEG C of vacuum-dryings, obtain modification by copolymerization resol P08M.Performance sees below table.
Embodiment 9(resol P09, modified phenolic resins P09M)
DMAC (the N adding 894g and cross through anhydrous sodium sulfate drying is with in the four-hole boiling flask of temperature control heating, mechanical stirring, condensing reflux and nitrogen protection device at 2000 ml; N-N,N-DIMETHYLACETAMIDE) and 200.0g resol P09 (commercial product code: MV4080G; m/p=60/40; Mw ≈ 5000); nitrogen adds 1.0g dibutyl tin laurate after protecting 60 DEG C of heated and stirred to dissolution of solid; then 157.6gMOI(methylacryoyloxyethyl isocyanic ester is slowly instilled); react 4 hours, until disappeared by peak, infrared spectra detection of active isocyanate group 2275 place.
63.1g N-4ASMI [chemical name: N-4 (sulfoamido phenyl) maleimide] is added, the DMAC that 157.8 g are dried, 2.1gAIBN (Diisopropyl azodicarboxylate), 70 DEG C of reaction reaction end after 23 hours in above-mentioned reaction solution.Reactant is separated out in deionized water, washs, 40 DEG C of vacuum-dryings, obtain modification by copolymerization resol P09M.Performance sees below table.
Embodiment 10(resol P10, modified phenolic resins P10M)
Temperature control heating is with at 2000 ml, mechanical stirring, DMAC (the N that 726.8g crosses through anhydrous sodium sulfate drying is added in the four-hole boiling flask of condensing reflux and nitrogen protection device, N-N,N-DIMETHYLACETAMIDE) and 200.0g resol P10 (commercial product code: EP30B20G, m/p/mx=60/30/10, Mw ≈ 9000), nitrogen adds 1.0g dibutyl tin laurate after protecting 60 DEG C of heated and stirred to dissolution of solid, then 105.1gMOI(methylacryoyloxyethyl isocyanic ester is slowly instilled), react 4 hours, until disappeared by peak, infrared spectra detection of active isocyanate group 2275 place.
164.3g N-4ASMI [chemical name: N-4 (sulfoamido phenyl) maleimide] is added, the DMAC that 410.8g is dried, 2.4gAIBN (Diisopropyl azodicarboxylate), 70 DEG C of reaction reaction end after 23 hours in above-mentioned reaction solution.Reactant is separated out in deionized water, washs, 40 DEG C of vacuum-dryings, obtain modification by copolymerization resol P10M.Performance sees below table.
Embodiment 11(resol P11, modified phenolic resins P11M)
Temperature control heating is with at 2000 ml, mechanical stirring, DMAC (the N that 729.8 g cross through anhydrous sodium sulfate drying is added in the four-hole boiling flask of condensing reflux and nitrogen protection device, N-N,N-DIMETHYLACETAMIDE) and 200.0g resol P11 (commercial product code: MXP5560BF, mC/mC/phenol=30/20/50, Mw ≈ 8000), nitrogen adds 1.0g dibutyl tin laurate after protecting 60 DEG C of heated and stirred to dissolution of solid, then 91.9gMOI(methylacryoyloxyethyl isocyanic ester is slowly instilled), react 4 hours, until disappeared by peak, infrared spectra detection of active isocyanate group 2275 place.
73.0g N-4HPMI [chemical name: N-4 (hydroxy phenyl) maleimide] is added, the DMAC that 182.5 g are dried, 1.8gAIBN (Diisopropyl azodicarboxylate), 70 DEG C of reaction reaction end after 23 hours in above-mentioned reaction solution.Reactant is separated out in deionized water, washs, 40 DEG C of vacuum-dryings, obtain modification by copolymerization resol P11M.Performance sees below table.
Embodiment 12(resol P12, modified phenolic resins P12M)
Temperature control heating is with at 5000 ml, mechanical stirring, DMAC (the N that 1055.8g crosses through anhydrous sodium sulfate drying is added in the four-hole boiling flask of condensing reflux and nitrogen protection device, N-N,N-DIMETHYLACETAMIDE) and 200.0g resol P12 (commercial product code: EPR3050G, m/p=50/50, Mw ≈ 6500), nitrogen adds 1.0g dibutyl tin laurate after protecting 60 DEG C of heated and stirred to dissolution of solid, then 222.3gMOI(methylacryoyloxyethyl isocyanic ester is slowly instilled), react 4 hours, until disappeared by peak, infrared spectra detection of active isocyanate group 2275 place.
The DMAC that 430.4g N-4HPMI [chemical name: N-4 (hydroxy phenyl) maleimide] 1076 g are dried is added, 4.3gAIBN (Diisopropyl azodicarboxylate), 70 DEG C of reaction reaction end after 23 hours in above-mentioned reaction solution.Reactant is separated out in deionized water, washs, 40 DEG C of vacuum-dryings, obtain modification by copolymerization resol P12M.Performance sees below table.
Embodiment 13(resol P13, modified phenolic resins P13M)
DMAC (the N adding 587.4 g and cross through anhydrous sodium sulfate drying is with in the four-hole boiling flask of temperature control heating, mechanical stirring, condensing reflux and nitrogen protection device at 1000 ml; N-N,N-DIMETHYLACETAMIDE) and 200.0g resol P03 (commercial product code: TR4020G; m/p=60/40; Mw ≈ 13000); nitrogen adds 1.0g dibutyl tin laurate after protecting 60 DEG C of heated and stirred to dissolution of solid; then 24.2g M1(allyl group monoisocyanates is slowly instilled); react 4 hours, until disappeared by peak, infrared spectra detection of active isocyanate group 2275 place.
24.9g MI(maleimide is added in above-mentioned reaction solution), the DMAC that 66.5 g are dried, 1.3gAIBN (Diisopropyl azodicarboxylate), 70 DEG C of reaction reaction end after 23 hours.Reactant is separated out in deionized water, washs, 40 DEG C of vacuum-dryings, obtain modification by copolymerization resol P13M.Performance sees below table.
Embodiment 14(resol P14, modified phenolic resins P14M)
Temperature control heating is with at 2000 ml, mechanical stirring, DMAC (the N that 738.6 g cross through anhydrous sodium sulfate drying is added in the four-hole boiling flask of condensing reflux and nitrogen protection device, N-N,N-DIMETHYLACETAMIDE) and 200.0g resol P11 (commercial product code: MXP5560BF, mC/mC/phenol=30/20/50, Mw ≈ 8000), nitrogen adds 1.0g dibutyl tin laurate after protecting 60 DEG C of heated and stirred to dissolution of solid, then slowly 104.9gM3(4-methylpropenyl-penylene based isocyanate is instilled), react 4 hours, until disappeared by peak, infrared spectra detection of active isocyanate group 2275 place.
76.2g N-4HPMI [chemical name: N-4 (hydroxy phenyl) maleimide] is added, the DMAC that 182.5 g are dried, 1.8gAIBN (Diisopropyl azodicarboxylate), 70 DEG C of reaction reaction end after 23 hours in above-mentioned reaction solution.Reactant is separated out in deionized water, washs, 40 DEG C of vacuum-dryings, obtain modification by copolymerization resol P11M.Performance sees below table.
Use above-mentioned unmodified resol P01-P14 respectively, ammonia esterification modification hybrid phenol-formaldehyde resin P01M-P14M, make comparative example and embodiment positive heat-sensitive sensitive lithographic plate that heat susceptible coating contains above-mentioned resin.
Version base process: the present invention's version base used is through electrolyzing and coarsening and anodic oxidation and aluminium plate base after carrying out sealing pores, and its medullary ray average boldness is at 0. 2-0. 6 u m.Preferably 0. 3-0. 5 u m.Such version base obtains 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 more than 99%.Suitable aluminium plate base is (but lose be limited to this): iron accounts for 0. 1%-0. 5%, silicon accounts for 0.03%-0.3%, copper accounts for 0. 003 %-0. 03 %, and titanium accounts for 0.01%-0.l%.Electrolyzing and coarsening electrolytic solution used can be acid, alkali or the aqueous solution of salt or the aqueous solution containing organic solvent.Wherein, electrolytic solution is made with the aqueous solution of hydrochloric acid, nitric acid or their salt better.First aluminium plate is placed in the aqueous solution of sodium hydroxide, potassium hydroxide, sodium carbonate, water glass etc. of 1 %-30%, at the temperature of 20-80 DEG C, carries out the chemical corrosion of 5-250 second.Then in the nitric acid or sulfuric acid of 10%-30% with the temperature of 20-70 DEG C in and, to remove grey matter.Like this through the aluminium plate of clean, 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 ㎡, 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.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 1-10 g/ ㎡.The oxide film of such formation has higher oxide film micropore usually, and adsorptive power is comparatively strong, is easy to adhere to foul.So usually also need to carry out sealing pores.Sealing pores can use various method, is good to reach the 50-80% volume of closed oxide film micropore, simultaneously hydrophilicity-imparting treatment.
The maximum absorption wavelength scope of infrared absorbing compounds contained by heat susceptible coating is 780-1100nm, be 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 pigment and dyestuff etc., addition is the 0.5%-15% of total solid matters weight.
Heat susceptible coating is containing dissolution inhibitor, and it contains polar group, can strengthen the hydrogen bonded intensity between resin (as resol), reduces the solubleness of unexposed area layer, and it promotes the solubleness of ir radiation district layer under protonic acid effect simultaneously.Dissolution inhibitor comprises low molecule quaternary ammonium salt, resol, sulphonate, phosphoric acid ester, aromatic carboxylic acid's ester, lactone ketone, aromatic hydrocarbons two sulfone, poly-alkoxyl group ether particularly polyethylene glycols etc.Addition is the 1%-20% of total solid matters weight.
Heat susceptible coating contains Thermal acid generators, and heat can discharge strong protonic acid, can reduce the association intensity of dissolution inhibitor and resol.Thermal acid generators comprises salt compounded of iodine class, sulfosalt class, pyridine salt, sulfonic acid esters, phosphoric acid ester, alicyclic ring ethers, triazines etc.The addition of Thermal acid generators is the 1%-30% of total solid matters weight.
Heat susceptible coating is containing dissolution accelerator, and it can improve dissolving sensitivity.Dissolution accelerator comprises organic acid, acid anhydrides, phenols etc.As sulfonic acid, phosphoric acid, alkyl benzene sulphonate (ABS), hexyloxy benzoic acid diacid, lauric acid, xitix, diacetyl oxide, Tetra hydro Phthalic anhydride, maleic anhydride, chloromaleic acid acid anhydride, succinyl oxide, dihydroxyphenyl propane, p-NP, to oxyethyl group phenol, 2,3,4-trihydroxy-benzophenone, 4-hydroxy benzophenone etc., the addition of dissolution accelerator is the 0.1%-10% of total solid matters weight.
Heat susceptible coating contains layer tinting material, and it comprises: methyl violet, ethyl violet, Viola crystallina, purple in crystallization, victoria blue, glossy dark green, oil blue, oil yellow, rhodamine B, methyl violet rowland, malachite green, methylene blue, triazines etc.Layer color additive is the 0.1%-10% of total solid matters weight.
Heat susceptible coating contains tensio-active agent, can select nonionogenic tenside, amphoterics, silicon-containing surfactant, fluorochemical surfactant etc.As betaines, stearin class, Sorbic Acid palm fibre grease class, polysiloxane-based, poly-fluoroalkyl ethers.The addition of tensio-active agent is the 0.01%-5% of total solid matters weight.
Prepare photosensitive liquid solvent to comprise: 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 use with pure substance form or form of mixtures.The solid content of coating mixture is generally 2-50% (weight).
Usually with this field, oneself knows that technology coating (as cutter painting, blade coating, bar painting, roller coat, extrusion, coiling rod are coated with) is on version base to photosensitive composition of the present invention.Photosensitive composition of the present invention is dissolved in suitable solvent or/and in water, is made into coating fluid.
Use above-mentioned unmodified resol P01-P14, ammonia esterification modification hybrid phenol-formaldehyde resin P01M-P14M, make the positive heat-sensitive sensitive lithographic plate 1-sensitive lithographic plate 24 that heat susceptible coating contains above-mentioned resin.
Positive heat-sensitive sensitive lithographic plate coating formula:
Photosensitive liquid (each component by weight)
Resol (individually using P01-P12, P01M-P12M) 71
Acidogenic agent (4,4'-dimethyl diphenyl salt compounded of iodine hexafluorophosphate, the photosensitive research institute in Shenyang) 10
Resistance solvent NS-5000 (Lucky Huaguang Graphics Co., Ltd.) 8
Infrared absorbing agents ADS830AT 6
Dissolution accelerator (tosic acid) 2
Tensio-active agent (BYK306) 1
Methyl violet (CI42535) 2
1-methoxy-2-propanol 900
The above-mentioned photosensitive liquid of extrusion coated on above-mentioned version base, then at 120 DEG C dry 60 seconds, obtains the dry coating weight of 1.8g/ ㎡.
Solvent resistance is investigated: above-mentioned plate sample to be immersed in respectively in ethylene glycol butyl ether 80% aqueous solution 20 minutes and Virahol 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, MASTER VIEW MV-CTP scouring machine, measures plate development adaptability and site performance.
Pressrun is investigated: normally printed (Beiren four look four drives high speed rotary press) by machine on above-mentioned plate sample, investigate its pressrun.
Plate performance sees attached list.
Shown by the application result of subordinate list, temperature-sensitive sensitive lithographic plate is used for containing ammonia esterification modification hybrid phenol-formaldehyde resin of the present invention, obviously can strengthen solvent resistant performance and the pressrun of temperature-sensitive version, this is because the ammonia ester bond of strong polarity exists in ammonia esterification modification hybrid phenol-formaldehyde resin, sensitive lithographic plate has strong, the tough and tensile advantage of coating adhesion; Again because second time linear polymerization hydridization, in resol, introduce the unique construction unit containing the molten group of alkali, improve resistance to dissolubility and the wear resistance of resin, the caustic solubility of resol is unaffected simultaneously.
Table 1: plate application performance table
Above-mentioned all embodiment plate development adaptability and site performance all meet print request.
Claims (4)
1. an ammonia esterification modification hybrid phenol-formaldehyde resin, it is characterized in that: it is by phenolic hydroxyl group ammonia esterification grafting vinyl monoisocyanates by linear phenolic resin, then as high polymer monomer separately or and other vinyl monomer carry out the hybrid phenol-formaldehyde resin that second time free radical linear polymerization obtains, ammonia esterification modification hybrid phenol-formaldehyde resin weight-average molecular weight is 7500-150000; Softening temperature is 80-220 DEG C;
Described vinyl monoisocyanates has following general structure:
In formula, R
1for hydrogen atom or methyl, R
2for ester group, penylene base or carbon-carbon single bond, r is the integer of 1-3, and phenolic hydroxyl group ammonia graft esterification rate is 10-90%;
Other described vinyl monomer is at least one contained in structure in the vinyl monomer of sulfoamido or reactive maleimide, and its weight accounts for the 10-50% of copolymerization weight.
2. ammonia esterification modification hybrid phenol-formaldehyde resin according to claim 1, is characterized in that: described linear phenolic resin is phenol, p-cresol, meta-cresol and composition thereof and the linear condensation product of formaldehyde, and molecular weight is 2500-14000.
3. the preparation method of ammonia esterification modification hybrid phenol-formaldehyde resin according to claim 1, it is characterized in that: by linear phenolic resin in reaction solvent, under nitrogen protection condition, heated and stirred adds catalyzer after linear phenolic resin dissolves, then vinyl monoisocyanates is dripped, react to ammonia esterification terminal at 40-120 DEG C, unsaturated monoisocyanates and phenolic hydroxyl group molar ratio are 0.05-0.95, and catalyst levels is the 0.005-10% of unsaturated monoisocyanates monomer weight; Then as high polymer monomer separately or and other vinyl monomer carry out the hybrid phenol-formaldehyde resin that second time free radical linear polymerization obtains.
4. the preparation method of ammonia esterification modification hybrid phenol-formaldehyde resin according to claim 3, is characterized in that: described linear phenolic resin is phenol, p-cresol, meta-cresol and composition thereof and the linear condensation product of formaldehyde, and molecular weight is 2500-14000.
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