CN102504073A - 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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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 with ammonia esterification modification hybrid phenol-formaldehyde resin and preparation method thereof.
Background technology
Lithography technique moves towards CTP technology (being called for short the CTP technology) from traditional laser photo film copy PS platemaking technology comprehensively, and the CTP plate is also popularized gradually.CTP plate kind is a lot, and that relatively popularizes comprises diffusion of silver salt CTP plate, UV-CTP version, purple laser polymerization CTP plate, thermal CTP plate material etc.Wherein most popular is thermal CTP plate material.At present, further improve the performance of heat-sensitive CTP plate, the solvent resistance and the Nai Yin ability that particularly improve plate are the thermal CTP plate material hot of research and development.
The anti-solvent of plate is meant the corrosion of the organic solvent in the anti-various printing chemical of printing plate, like washing oil, fountain solution, gum-solution, forme preserving agent, forme sanitising agent, the particularly corrosion of using in the printing of UV printing ink washing oil of printing ink.
Plate wear resistance and solvent resistance have certain cognation, but not absolute.In general, solvent resistance plate preferably 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 printing ink of anti-UV.
The solvent resistance of raising heat-sensitive CTP plate plate and the method for Nai Yin ability are a lot; Wherein one of most important method is exactly the particularly exploitation of functional film-forming resin of printing plate organism; For example Kodak's patent CN101321632A is disclosed introduces phosphoric acid or diamantane side group at polymkeric substance, improves the chemical-resistant of plate.
Resol is a kind of important temperature-sensitive version film-forming resin, can improve the solvent resistance and the pressrun of temperature-sensitive version through modification, the modification of resol.
Printing plate generally is to carry out modification through the distant pawl group of phenolic hydroxyl group with modification, the modification of caustic solubility resol, for example EP-A 0934822 disclosed resol phenolic hydroxyl group and sulfonic group or carboxy moiety esterification modification.
The EP of Agfa Corp. [31] 02102446.8, CN1688441A disclose and a kind ofly through the distant pawl group of phenolic hydroxyl group resol have been carried out diazonium salt grafted method of modifying, are used for improving the chemical resistance of temperature-sensitive version.The Ai Kefa disclosed method is that resol is carried out the diazonium salt graft modification, forms azo-aromatic yl group (N=N-Q group, Q are aromatic group), improves chemical resistance of coating.
Fujiphoto [32] 2004.3.11 [33] JP [31] 2004-069478 has proposed main chain to have phenol skeleton and urea key (temperature-sensitive version resin NHCONH-) has solvent resistance.
Kodak proposes at WO2004/033206, in the macromolecule resin side chain, introduces the barbituric acid group, can obviously improve the solvent resistance and the wear resistance of plate coating.Kodak discloses a kind of method of passing through the phenolic hydroxyl group grafting barbituric acid group of resol.
Kodak discloses a kind of QHB modified phenolic resins at WO2004/033206 among the CN200380104739.7.The 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 i.e. second polymeric layer in multilayer heat-sensitive version upper strata, to improve the wear resistance of plate.
Fujiphoto JP 2000-7-13 2000-213142, CN01120259 have introduced a kind of Lighographic printing plate precursor; Contain three-dimensional POLYMETHYLENE POLYPHENYLISOCYANATE precrosslink structure and comprise the polymkeric substance of hydrophilic grafted chain, three-dimensional POLYMETHYLENE POLYPHENYLISOCYANATE precrosslink structure has improved the pressrun of printing plate.
Above-mentioned STUDY ON THE MODIFICATION OF PENOLIC RESIN, because phenolic hydroxyl group is partially enclosed, the caustic solubility of resin and plate more or less will arrive influenced.
Summary of the invention
The objective of the invention is to solve the anti-solvent ability of temperature-sensitive version that exists in the existing temperature-sensitive platemaking technology and the shortcoming of Nai Yin ability; Particularly improve the partially enclosed of that the anti-solvent ability of plate and Nai Yin ability exist because phenolic hydroxyl group through phenolic resin modified method, the caustic solubility of resin and plate will arrive affected shortcoming.A kind of brand-new ammonia esterification modification hybrid phenol-formaldehyde resin and preparation method thereof is provided, and the resol after the modification is used for heat-sensitive CTP plate and has good film-forming property, anti-solvent, advantage that pressrun is high, and the caustic solubility of plate is unaffected.
For realizing above-mentioned purpose, the present invention adopts following technical scheme:
Ammonia esterification modification hybrid phenol-formaldehyde resin of the present invention; It is through phenolic hydroxyl group ammonia esterification grafting vinyl monoisocyanates by linear phenolic resin; Carry out the hybrid phenol-formaldehyde resin that the second time, the radical linear polymerization obtained separately or with other vinyl monomer as high polymer monomer then, ammonia esterification modification hybrid phenol-formaldehyde resin weight-average molecular weight is 7500-150000; Softening temperature is 80-220 ℃.
Described linear phenolic resin is the linear condensation product of phenol, p-cresol, meta-cresol and composition thereof and formaldehyde, and molecular weight is 2500-14000.
Described vinyl monoisocyanates has following general structure:
In the formula, R
1Be Wasserstoffatoms or methyl, R
2Be 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%.
Described other vinyl monomer is to contain at least a in the vinyl monomer that sulfoamido or active maleimide and N-thereof replace the caustic solubility verivate in the 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; With linear phenolic resin in reaction solvent; Heated and stirred to linear phenolic resin dissolving back adds catalyzer under the nitrogen protection condition, drips the vinyl monoisocyanates then, under 40-120 ℃, reacts to ammonia esterification terminal point; 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; Carry out the hybrid phenol-formaldehyde resin that the second time, the radical linear polymerization obtained separately or with other vinyl monomer as high polymer monomer then.
Elaborate in the face of the present invention down:
1, through the ammonia esterification, in resol, introduce strong polarity ammonia ester bond, introduce two keys simultaneously;
2, then with containing of ammonia esterification two keys the independent homopolymerization of resol radical or and other contain the extraordinary monomer copolymerization of caustic solubility group, form ammonia esterification modification hybrid phenol-formaldehyde resin;
3, introduce during copolymerization and contain alkali and dissolve group and the special wear-resisting group of anti-the solvent.
Strengthen the molecular resin amount owing to introduced strong polarity ammonia ester bond, the special wear-resisting group of anti-solvent the and repolymerization hydridization in the resin, the anti-solvent of plate, pressrun got and significantly improved.Simultaneously, for the second time free-radical polymerizedly introduced in structure that alkali dissolves that group has improved after the resol graft modification in the past that phenolic hydroxyl group reduces or caused the affected shortcoming of plate caustic solubility greatly because of the molecule quantitative change.
Synthetic route is in two steps:
1, at first passes through phenolic hydroxyl group ammonia esterification grafting vinyl monoisocyanates by linear phenolic resin;
2, with the resol behind the grafting vinyl monoisocyanates, as high polymer monomer separately or and other extraordinary monomer that contains the caustic solubility group carry out the radical linear polymerization second time.
It below is 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 through phenolic hydroxyl group ammonia esterification grafting vinyl monoisocyanates, carry out as high polymer monomer then that the radical linear polymerization obtains the second time separately or with other vinyl monomer.
Linear phenolic resin of the present invention is that phenols and aldehydes carry out the linear product that condensation reaction obtains.
Specifiable phenols example have phenol, m-cresol, p-cresol ,/to mixed methyl phenol, pyrogallol, isopropyl-phenol, tert.-butyl phenol, tert.-amyl phenol, hexylphenol, cyclohexylphenol, 3-methyl-4-chloro-uncle's 6-butylphenol and phenolic group verivate such as hydroxy styrenes or the like.
Specifiable aldehydes example alkanoic has formaldehyde, acetaldehyde, propenal, crotonaldehyde and aromatic series, heterocycle family aldehyde or the like
Linear phenolic resin of the present invention is preferentially selected 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 for use.
Linear phenolic resin of the present invention is preferentially selected the linear condensation product of phenol, p-cresol, meta-cresol and composition thereof and formaldehyde for use, and synthesis technique can be referring to " new test chemistry " the 300th of a polymer chemistry piece of writing (1993, Japanese ball is apt to press).
The synthetic preferred 1000-100000 of linear phenolic resin weight-average molecular weight of the present invention, 2000-50000 more preferably most preferably is and is 2500-14000.
Commercial linear phenolic resin can companies such as one-tenth, Switzerland DKSH, Bakelite, Clariant GmbH, B.P. chemistry be buied from sky, Weihai.
Synthetic used unsaturated monoisocyanates (code name M) structural formula of ammonia esterification modification hybrid phenol-formaldehyde resin of the present invention grafting is:
R
1Be Wasserstoffatoms or methyl, R
2Be ester group, penylene base or carbon-carbon single bond etc., r is the integer of 1-3.
Detailed example is stated structural formula as follows, but the present invention is not limited to the structural formula of following M1-M3.
M1
M2
M3
Polymkeric substance ammonia graft esterification reaction synthetic of the present invention, unsaturated monoisocyanates and the preferred 0.05-0.95 of phenolic hydroxyl group molar ratio, optimum is 0.1-0.9, and perhaps phenolic hydroxyl group ammonia graft esterification rate is preferred 5-95%, and optimum does
10-90%。
The reaction solvent of the unsaturated monoisocyanates of grafting must be the solvent that does not contain active proton hydrogen, as 1, and 4-dioxane, N, dinethylformamide, N,N-DIMETHYLACETAMIDE, methylethylketone, pimelinketone, ETHYLE ACETATE, toluene etc., or their mixture.Preferably adopt ammonia ester level N, N,N-DIMETHYLACETAMIDE or pimelinketone.
The catalyzer of the unsaturated monoisocyanates of grafting such as lead octoate 36, stannous octoate, dibutyl tin laurate, triethylenediamine, cobalt octoate, iron octoate etc. all can; 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%.40-120 ℃ of graft reaction temperature is preferably in 60-110 ℃.
The ammonia esterification is accomplished the judgement of terminal point: the ammonia esterification is accomplished the sign of terminal point: disappear through peak, ir spectra detection of active NCO 2275 place; Or liquid phase gel chromatography detection of active NCO disappears the disappearance of the reverse volumetry detection of active of also available Di-n-Butyl Amine NCO.
Resol after the ammonia esterification and since grafting activity double key, also can be directly as the photosensitive resin and the film-forming resin of polymerizability negativity plate.
The resol further hydridization of the present invention after with the ammonia esterification.
Linear phenolic resin is through behind the phenolic hydroxyl group ammonia esterification grafting vinyl monoisocyanates; Can be used as the independent homopolymerization of high polymer monomer or carry out the radical linearity copolymerization second time with other vinyl monomer, polymerization obtains ammonia esterification modification hybrid phenol-formaldehyde resin of the present invention.
Homopolymerization: the resol behind the ammonia graft esterification is as the independent homopolymerization of high polymer monomer, and the hybrid phenol-formaldehyde resin that obtains is as temperature-sensitive version film-forming resin, and it still is phenolic hydroxyl group that its alkali dissolves group.Because the reaction of ammonia graft esterification will consume the part phenolic hydroxyl group; Certainly will influence the alkali capacitive of the hybrid phenol-formaldehyde resin that after polymerization obtains; So ammonia graft esterification rate can not be too high, the resol before the grafting selects for use hydroxyl value bigger as far as possible; The resol that caustic solubility is good is in order to avoid influence the caustic solubility of hybrid resin.
Copolymerization: the resol behind the ammonia graft esterification can carry out the linear copolymerization of the radical second time by other vinyl monomer as high polymer monomer.
Other vinyl monomer can be selected the monomer of any free redical copolymerization for use in theory, as contains following monomer and verivate 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 or the like.
The monomer of preferentially selecting for use as the present invention; Should possess alkali and dissolve group; Can in hybrid resin, form side group alkali after the copolymerization hydridization and dissolve group; The caustic solubility of ammonia graft esterification reaction consumes part phenolic hydroxyl group loss can remedy owing to can remedy after polymerization resol molecular weight simultaneously and increase the caustic solubility influence that brings.
The vinyl monomer that possesses the caustic solubility group, specifiable as contain the vinyl monomer that group such as carboxyl, phenolic hydroxyl group, sulfonic group, phosphate, sulfoamido, active imide base and alkali thereof dissolve verivate.
As the monomer that the present invention preferentially selects for use, the above-mentioned vinyl monomer that possesses the caustic solubility group also can be further preferred.For solvent resistance and the wear resistance that increases hybrid resin; Preferably the big perhaps chemicals-resistant of polarity corrodes or the good known special engineering plastics polymerization single polymerization monomer of wear resistance; Possess simultaneously in the above-mentioned monomer this specific character monomer we preferably contain the vinyl monomer that sulfoamido or active maleimide and N-thereof replace the caustic solubility verivate, wherein the N-substituting group of maleimide must have caustic solubility.
Contain the vinyl monomer that sulfoamido or active maleimide and N-thereof replace the caustic solubility verivate, specifiable have N-(4-sulfoamido benzene) USAF RH-1, N-(4-ethyl sulfonamide base benzene) USAF RH-1, N-(4-benzenesulfonyl amine phenyl) USAF RH-1, N-(4-carboxyl benzene) USAF RH-1 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.
Optional random copolymerization of copolyreaction or block copolymerization, preferred random copolymerization.The initiator of radical polymerization comprises superoxide such as ditertiary butyl peroxide, benzoyl peroxide; Persulphate such as Potassium Persulphate, azo cpd such as Diisopropyl azodicarboxylate etc.; Reaction can be adopted 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 accomplish; Preferably adopt single stage method synthetic, adopt single stage method, but reaction solvent must be the solvent that does not contain active proton hydrogen recited above; As 1; 4-dioxane, N, dinethylformamide, N,N-DIMETHYLACETAMIDE, methylethylketone, pimelinketone, ETHYLE ACETATE, toluene etc., or their mixture.Preferably adopt ammonia ester level N, N,N-DIMETHYLACETAMIDE or pimelinketone.40-110 ℃ of copolyreaction temperature is preferably in 50-100 ℃.
For the second time free-radical polymerized polymerization degree n ' control be the key that influences resin property; Can measure the molecular resin amount through gel permeation chromatography GPC; Estimation copolymerization for the second time polymerization degree n ' ≈ Mw (modified)/Mw (no-modified); Wherein Mw (modified) is resol weight-average molecular weight after the modification, and Mw (no-modified) so that control the Raolical polymerizable condition, adjusts resin property for resol weight-average molecular weight after the modification.
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 ℃, is preferably 50-250 ℃, most preferably is 80-220 ℃.
Ammonia esterification modification hybrid phenol-formaldehyde resin of the present invention, its purposes are to make positive thermosensitive CTP version.
Contain ammonia esterification modification hybrid phenol-formaldehyde resin of the present invention and be used for temperature-sensitive flat stamping version; Can obviously strengthen the good solubility-resistence ability and the pressrun of temperature-sensitive version; This is that the flat stamping version has strong, the tough and tensile advantage of coating adhesion because strong polar ammonia ester bond exists in the ammonia esterification modification hybrid phenol-formaldehyde resin; Because of the linear polymerization hydridization second time, in resol, introduced the unique construction unit that contains the molten group of alkali again, improved the anti-dissolubility and the wear resistance of resin, the caustic solubility of resol is unaffected simultaneously.
Embodiment
Be synthetic instance of the present invention below, but the present invention is not limited to following instance.
12 sample P 01-P12 carry out ammonia esterification hybrid modification to resol, obtain corresponding modified product P01M-P12M respectively.
Resol P01-P12: all available from Switzerland DKSH.Comonomer is all competed available from the 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)
In the four-hole boiling flask of 1000 ml band temperature control heating, mechanical stirring, condensing reflux and nitrogen protection device, add the DMAC (N that 565.7 g cross through anhydrous sodium sulfate drying; The N-N,N-DIMETHYLACETAMIDE) and 200.0g resol P01 (commercial product code: MV4020G; M/p=60/40; Mw ≈ 14000), nitrogen protects 60 ℃ of heated and stirred to solid dissolving backs and adds the 1.0g dibutyl tin laurate, slowly splashes into 26.3gMOI (methylacryoyloxyethyl isocyanic ester) then; Reacted 4 hours, up to disappearing through peak, ir spectra detection of active NCO 2275 place.
In above-mentioned reaction solution, add 1.2gAIBN (Diisopropyl azodicarboxylate), 23 hours afterreactions of 70 ℃ of reactions finish.Reactant is separated out in deionized water, washed, and 40 ℃ of vacuum-dryings obtain homopolymerization modified phenolic resins P01M.The performance table of seeing after.
Embodiment 2 (resol P02, modified phenolic resins P02M)
In the four-hole boiling flask of 1500 ml band temperature control heating, mechanical stirring, condensing reflux and nitrogen protection device, add the DMAC (N that 1091 g cross through anhydrous sodium sulfate drying; The N-N,N-DIMETHYLACETAMIDE) and 200.0g resol P02 (commercial product code: EPR6040A; M/p=40/60; Mw ≈ 2500), nitrogen protects 60 ℃ of heated and stirred to solid dissolving backs and adds the 1.0g dibutyl tin laurate, slowly splashes into 236.4gMOI (methylacryoyloxyethyl isocyanic ester) then; Reacted 4 hours, up to disappearing through peak, ir spectra detection of active NCO 2275 place.
In above-mentioned reaction solution, add 2.2gAIBN (Diisopropyl azodicarboxylate), 23 hours afterreactions of 70 ℃ of reactions finish.Reactant is separated out in deionized water, washed, and 40 ℃ of vacuum-dryings obtain homopolymerization modified phenolic resins P02M.The performance table of seeing after.
Embodiment 3 (resol P03, modified phenolic resins P03M)
In the four-hole boiling flask of 1000 ml band temperature control heating, mechanical stirring, condensing reflux and nitrogen protection device, add the DMAC (N that 598.5 g cross through anhydrous sodium sulfate drying; The N-N,N-DIMETHYLACETAMIDE) and 200.0g resol P03 (commercial product code: TR4020G; M/p=60/40; Mw ≈ 13000), nitrogen protects 60 ℃ of heated and stirred to solid dissolving backs and adds the 1.0g dibutyl tin laurate, slowly splashes into 39.4gMOI (methylacryoyloxyethyl isocyanic ester) then; Reacted 4 hours, up to disappearing through peak, ir spectra detection of active NCO 2275 place.
In above-mentioned reaction solution, add 26.6g MI (maleimide), the dry DMAC that crosses of 66.5 g, 1.3gAIBN (Diisopropyl azodicarboxylate), 23 hours afterreactions of 70 ℃ of reactions finish.Reactant is separated out in deionized water, washed, and 40 ℃ of vacuum-dryings obtain modification by copolymerization resol P03M.The performance table of seeing after.
Embodiment 4 (resol P04, modified phenolic resins P04M)
In the four-hole boiling flask of 3000 ml band temperature control heating, mechanical stirring, condensing reflux and nitrogen protection device, add the DMAC (N that 1058.3 g cross through anhydrous sodium sulfate drying; The N-N,N-DIMETHYLACETAMIDE) and 200.0g resol P04 (commercial product code: EPR5000B; MC/pC=50/50; Mw ≈ 3000), nitrogen protects 60 ℃ of heated and stirred to solid dissolving backs and adds the 1.0g dibutyl tin laurate, slowly splashes into 223.3gMOI (methylacryoyloxyethyl isocyanic ester) then; Reacted 4 hours, up to disappearing through peak, ir spectra detection of active NCO 2275 place.
In above-mentioned reaction solution, add 423.3g MI (maleimide), the dry DMAC that crosses of 1058.3 g, 4.2gAIBN (Diisopropyl azodicarboxylate), 23 hours afterreactions of 70 ℃ of reactions finish.Reactant is separated out in deionized water, washed, and 40 ℃ of vacuum-dryings obtain modification by copolymerization resol P04M.The performance table of seeing after.
Embodiment 5 (resol P05, modified phenolic resins P05M)
In the four-hole boiling flask of 2000 ml band temperature control heating, mechanical stirring, condensing reflux and nitrogen protection device, add the DMAC (N that 697g crosses through anhydrous sodium sulfate drying; The N-N,N-DIMETHYLACETAMIDE) and 200.0g resol P05 (commercial product code: PP3525G; P/phenol=35/65; Mw ≈ 11500), nitrogen protects 60 ℃ of heated and stirred to solid dissolving backs and adds the 1.0g dibutyl tin laurate, slowly splashes into 78.8gMOI (methylacryoyloxyethyl isocyanic ester) then; Reacted 4 hours, up to disappearing through peak, ir spectra detection of active NCO 2275 place.
In above-mentioned reaction solution, add 49.2g N-4ASAM [chemical name: N-4 (sulfoamido phenyl) acrylic amide], the dry DMAC that crosses of 123 g, 1.7gAIBN (Diisopropyl azodicarboxylate), 23 hours afterreactions of 70 ℃ of reactions finish.Reactant is separated out in deionized water, washed, and 40 ℃ of vacuum-dryings obtain modification by copolymerization resol P05M.The performance table of seeing after.
Embodiment 6 (resol P06, modified phenolic resins P06M)
In the four-hole boiling flask of 3000 ml band temperature control heating, mechanical stirring, condensing reflux and nitrogen protection device, add the DMAC (N that 958.3g crosses through anhydrous sodium sulfate drying; The N-N,N-DIMETHYLACETAMIDE) and 200.0g resol P06 (commercial product code: MV6020G; M/p=40/60; Mw ≈ 3800), nitrogen protects 60 ℃ of heated and stirred to solid dissolving backs and adds the 1.0g dibutyl tin laurate, slowly splashes into 183.9gMOI (methylacryoyloxyethyl isocyanic ester) then; Reacted 4 hours, up to disappearing through peak, ir spectra detection of active NCO 2275 place.
In above-mentioned reaction solution, add 206.7g N-4ASAM [chemical name: N-4 (sulfoamido phenyl) acrylic amide], the dry DMAC that crosses of 516.8 g, 3gAIBN (Diisopropyl azodicarboxylate), 23 hours afterreactions of 70 ℃ of reactions finish.Reactant is separated out in deionized water, washed, and 40 ℃ of vacuum-dryings obtain modification by copolymerization resol P06M.The performance table of seeing after.
Embodiment 7 (resol P07, modified phenolic resins P07M)
In the four-hole boiling flask of 2000 ml band temperature control heating, mechanical stirring, condensing reflux and nitrogen protection device, add the DMAC (N that 631.3 g cross through anhydrous sodium sulfate drying; The N-N,N-DIMETHYLACETAMIDE) and 200.0g resol P07 (commercial product code: EPR5010G; M/p=50/50; Mw ≈ 11000), nitrogen protects 60 ℃ of heated and stirred to solid dissolving backs and adds the 1.0g dibutyl tin laurate, slowly splashes into 52.5gMOI (methylacryoyloxyethyl isocyanic ester) then; Reacted 4 hours, up to disappearing through peak, ir spectra detection of active NCO 2275 place.
In above-mentioned reaction solution, add 63.1g N-4HPAM [chemical name: N-4 (hydroxy phenyl) acrylic amide], the dry DMAC that crosses of 157.8g, 1.6gAIBN (Diisopropyl azodicarboxylate), 23 hours afterreactions of 70 ℃ of reactions finish.Reactant is separated out in deionized water, washed, and 40 ℃ of vacuum-dryings obtain modification by copolymerization resol P07M.The performance table of seeing after.
Embodiment 8 (resol P08, modified phenolic resins P08M)
In the four-hole boiling flask of 3000 ml band temperature control heating, mechanical stirring, condensing reflux and nitrogen protection device, add the DMAC (N that 1025.5 g cross through anhydrous sodium sulfate drying; The N-N,N-DIMETHYLACETAMIDE) and 200.0g resol P08 (commercial product code: EPR6050G; M/p=40/60; Mw ≈ 4000), nitrogen protects 60 ℃ of heated and stirred to solid dissolving backs and adds the 1.0g dibutyl tin laurate, slowly splashes into 210.2gMOI (methylacryoyloxyethyl isocyanic ester) then; Reacted 4 hours, up to disappearing through peak, ir spectra detection of active NCO 2275 place.
In above-mentioned reaction solution, add 273.5g N-4HPAM [chemical name: N-4 (hydroxy phenyl) acrylic amide], the dry DMAC that crosses of 683.8 g, 3.4gAIBN (Diisopropyl azodicarboxylate), 23 hours afterreactions of 70 ℃ of reactions finish.Reactant is separated out in deionized water, washed, and 40 ℃ of vacuum-dryings obtain modification by copolymerization resol P08M.The performance table of seeing after.
Embodiment 9 (resol P09, modified phenolic resins P09M)
In the four-hole boiling flask of 2000 ml band temperature control heating, mechanical stirring, condensing reflux and nitrogen protection device, add the DMAC (N that 894g crosses through anhydrous sodium sulfate drying; The N-N,N-DIMETHYLACETAMIDE) and 200.0g resol P09 (commercial product code: MV4080G; M/p=60/40; Mw ≈ 5000), nitrogen protects 60 ℃ of heated and stirred to solid dissolving backs and adds the 1.0g dibutyl tin laurate, slowly splashes into 157.6gMOI (methylacryoyloxyethyl isocyanic ester) then; Reacted 4 hours, up to disappearing through peak, ir spectra detection of active NCO 2275 place.
In above-mentioned reaction solution, add 63.1g N-4ASMI [chemical name: N-4 (sulfoamido phenyl) maleimide], the dry DMAC that crosses of 157.8 g, 2.1gAIBN (Diisopropyl azodicarboxylate), 23 hours afterreactions of 70 ℃ of reactions finish.Reactant is separated out in deionized water, washed, and 40 ℃ of vacuum-dryings obtain modification by copolymerization resol P09M.The performance table of seeing after.
Embodiment 10 (resol P10, modified phenolic resins P10M)
In the four-hole boiling flask of 2000 ml band temperature control heating, mechanical stirring, condensing reflux and nitrogen protection device, add the DMAC (N that 726.8g crosses through anhydrous sodium sulfate drying; The N-N,N-DIMETHYLACETAMIDE) and 200.0g resol P10 (commercial product code: EP30B20G; M/p/mx=60/30/10; Mw ≈ 9000), nitrogen protects 60 ℃ of heated and stirred to solid dissolving backs and adds the 1.0g dibutyl tin laurate, slowly splashes into 105.1gMOI (methylacryoyloxyethyl isocyanic ester) then; Reacted 4 hours, up to disappearing through peak, ir spectra detection of active NCO 2275 place.
In above-mentioned reaction solution, add 164.3g N-4ASMI [chemical name: N-4 (sulfoamido phenyl) maleimide], the dry DMAC that crosses of 410.8g, 2.4gAIBN (Diisopropyl azodicarboxylate), 23 hours afterreactions of 70 ℃ of reactions finish.Reactant is separated out in deionized water, washed, and 40 ℃ of vacuum-dryings obtain modification by copolymerization resol P10M.The performance table of seeing after.
Embodiment 11 (resol P11, modified phenolic resins P11M)
In the four-hole boiling flask of 2000 ml band temperature control heating, mechanical stirring, condensing reflux and nitrogen protection device, add the DMAC (N that 729.8 g cross through anhydrous sodium sulfate drying; The N-N,N-DIMETHYLACETAMIDE) and 200.0g resol P11 (commercial product code: MXP5560BF; MC/mC/phenol=30/20/50; Mw ≈ 8000), nitrogen protects 60 ℃ of heated and stirred to solid dissolving backs and adds the 1.0g dibutyl tin laurate, slowly splashes into 91.9gMOI (methylacryoyloxyethyl isocyanic ester) then; Reacted 4 hours, up to disappearing through peak, ir spectra detection of active NCO 2275 place.
In above-mentioned reaction solution, add 73.0g N-4HPMI [chemical name: N-4 (hydroxy phenyl) maleimide], the dry DMAC that crosses of 182.5 g, 1.8gAIBN (Diisopropyl azodicarboxylate), 23 hours afterreactions of 70 ℃ of reactions finish.Reactant is separated out in deionized water, washed, and 40 ℃ of vacuum-dryings obtain modification by copolymerization resol P11M.The performance table of seeing after.
Embodiment 12 (resol P12, modified phenolic resins P12M)
In the four-hole boiling flask of 5000 ml band temperature control heating, mechanical stirring, condensing reflux and nitrogen protection device, add the DMAC (N that 1055.8g crosses through anhydrous sodium sulfate drying; The N-N,N-DIMETHYLACETAMIDE) and 200.0g resol P12 (commercial product code: EPR3050G; M/p=50/50; Mw ≈ 6500), nitrogen protects 60 ℃ of heated and stirred to solid dissolving backs and adds the 1.0g dibutyl tin laurate, slowly splashes into 222.3gMOI (methylacryoyloxyethyl isocyanic ester) then; Reacted 4 hours, up to disappearing through peak, ir spectra detection of active NCO 2275 place.
In above-mentioned reaction solution, add the dry DMAC that crosses of 430.4g N-4HPMI [chemical name: N-4 (hydroxy phenyl) maleimide] 1076 g, 4.3gAIBN (Diisopropyl azodicarboxylate), 23 hours afterreactions of 70 ℃ of reactions finish.Reactant is separated out in deionized water, washed, and 40 ℃ of vacuum-dryings obtain modification by copolymerization resol P12M.The performance table of seeing after.
Embodiment 13 (resol P13, modified phenolic resins P13M)
In the four-hole boiling flask of 1000 ml band temperature control heating, mechanical stirring, condensing reflux and nitrogen protection device, add the DMAC (N that 587.4 g cross through anhydrous sodium sulfate drying; The N-N,N-DIMETHYLACETAMIDE) and 200.0g resol P03 (commercial product code: TR4020G; M/p=60/40; Mw ≈ 13000), nitrogen protects 60 ℃ of heated and stirred to solid dissolving backs and adds the 1.0g dibutyl tin laurate, slowly splashes into 24.2g M1 (allyl group monoisocyanates) then; Reacted 4 hours, up to disappearing through peak, ir spectra detection of active NCO 2275 place.
In above-mentioned reaction solution, add 24.9g MI (maleimide), the dry DMAC that crosses of 66.5 g, 1.3gAIBN (Diisopropyl azodicarboxylate), 23 hours afterreactions of 70 ℃ of reactions finish.Reactant is separated out in deionized water, washed, and 40 ℃ of vacuum-dryings obtain modification by copolymerization resol P13M.The performance table of seeing after.
Embodiment 14 (resol P14, modified phenolic resins P14M)
In the four-hole boiling flask of 2000 ml band temperature control heating, mechanical stirring, condensing reflux and nitrogen protection device, add the DMAC (N that 738.6 g cross through anhydrous sodium sulfate drying; The N-N,N-DIMETHYLACETAMIDE) and 200.0g resol P11 (commercial product code: MXP5560BF; MC/mC/phenol=30/20/50; Mw ≈ 8000), nitrogen protects 60 ℃ of heated and stirred to solid dissolving backs and adds the 1.0g dibutyl tin laurate, slowly splashes into 104.9gM3 (4-methylpropenyl-penylene based isocyanate) then; Reacted 4 hours, up to disappearing through peak, ir spectra detection of active NCO 2275 place.
In above-mentioned reaction solution, add 76.2g N-4HPMI [chemical name: N-4 (hydroxy phenyl) maleimide], the dry DMAC that crosses of 182.5 g, 1.8gAIBN (Diisopropyl azodicarboxylate), 23 hours afterreactions of 70 ℃ of reactions finish.Reactant is separated out in deionized water, washed, and 40 ℃ of vacuum-dryings obtain modification by copolymerization resol P11M.The performance table of seeing after.
Use above-mentioned unmodified resol P01-P14 respectively, ammonia esterification modification hybrid phenol-formaldehyde resin P01M-P14M makes comparative example and embodiment positive heat-sensitive flat stamping version that the temperature-sensitive coating contains above-mentioned resin.
The version base is handled: the used version base of the present invention is through electrolyzing and coarsening and anodic oxidation and carries out sealing of hole and handle the back aluminium plate base that 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 through the method for various electrolyzing and coarsening.Aluminium plate base of the present invention is the high purity aluminium plate, and its aluminium content is preferably in more than 99%.Suitable aluminium plate base is (being limited to this but lose): iron accounts for 0. 1%-0. 5%, silicon accounts for 0.03%-0.3%, copper accounts for 0. 003 %-0. 03 %, and titanium accounts for 0.01%-0.l%.The used electrolytic solution of electrolyzing and coarsening can be the aqueous solution of acid, alkali or salt or the aqueous solution that contains organic solvent.Wherein, it is better to make electrolytic solution with the aqueous solution of hydrochloric acid, nitric acid or their salt.At first be placed on aluminium plate in the aqueous solution of sodium hydroxide, Pottasium Hydroxide, yellow soda ash, water glass etc. of 1 %-30%, under 20-80 ℃ temperature, carry out the 5-250 chemical corrosion of second.Then in the nitric acid of 10%-30% or sulfuric acid with 20-70 ℃ temperature neutralization, to remove grey matter.Like this through the aluminium plate of clean, under 10-6O ℃ temperature, with square wave, bench-type ripple or the sine wave etc. of positive and negative interaction variation, with the current density of 5-100A/d ㎡, electrolysis treatment 10-300 second in the electrolytic solution of nitric acid or hydrochloric acid.Then, carry out anodize through electrolytic aluminium plate.Sulfuric acid process is used in anodic oxidation usually.The vitriolic concentration of 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 sull of 1-10 g/ ㎡.The sull that forms like this has higher sull micropore usually, and adsorptive power is stronger, is easy to adhere to foul.So also need carry out sealing of hole usually handles.Sealing of hole is handled can use various methods, is good with the 50-80% volume that reaches sealing sull micropore, simultaneously hydrophilicity-imparting treatment.
The maximum absorption wavelength scope of the contained infrared absorbing compounds of temperature-sensitive coating is 780-1100nm; Be selected from carbon black, triarylamine dyestuff, 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 or the like, addition is the 0.5%-15% of total solid matters weight.
The temperature-sensitive coating contains dissolution inhibitor, and it contains polar group, can strengthen the hydrogen bonded intensity between the resin (like resol), reduces the solubleness of unexposed area figure layer, and it promotes the solubleness of ir radiation district figure layer under the protonic acid effect simultaneously.Dissolution inhibitor comprises low molecule quaternary ammonium salt, resol, sulphonate, SULPHOSUCCINIC ACID ESTER, aromatic carboxylic acid's ester, lactone ketone, aromatic hydrocarbons two sulfones, gathers particularly polyethylene glycols or the like of alkoxyl group ether.Addition is the 1%-20% of total solid matters weight.
The temperature-sensitive coating contains the thermic acidogenic agent, meets heat and can discharge strong protonic acid, can reduce the association intensity of dissolution inhibitor and resol.The thermic acidogenic agent comprises salt compounded of iodine class, sulfosalt class, pyridine salt, sulfonic acid esters, phosphoric acid ester, alicyclic ring ethers, triazines or the like.The addition of thermic acidogenic agent is the 1%-30% of total solid matters weight.
The temperature-sensitive coating contains dissolution accelerator, and it can improve dissolving sensitivity.Dissolution accelerator comprises organic acid, acid anhydrides, phenols or the like.Like sulfonic acid, phosphoric acid, alkyl benzene sulphonate(ABS), hexyloxy benzoic acid diacid, LAURIC ACID 99 MIN, 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 or the like, the addition of dissolution accelerator are the 0.1%-10% of total solid matters weight.
The temperature-sensitive coating contains figure layer tinting material, and it comprises: purple in the pyoktanin blue, ethyl violet, Viola crystallina, crystallization, victoria blue, glossy dark green, oil blue, oil yellow, rhodamine B, pyoktanin blue rowland, malachite green, methylene blue, triazines or the like.Figure layer tinting material addition is the 0.1%-10% of total solid matters weight.
The temperature-sensitive coating contains tensio-active agent, can select nonionogenic tenside, amphoterics, silicon-containing surfactant, fluorochemical surfactant etc. for use.As betaines, stearin class, Sorbic Acid palm fibre grease class, polysiloxane-based, gather the fluoroalkyl ethers.The addition of tensio-active agent is the 0.01%-5% of total solid matters weight.
Preparation sensitization liquid solvent comprises: acetone; Methyl ethyl ketone; Hexanaphthene; ETHYLE ACETATE; Ethylene dichloride; THF; Toluene; EGME; 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; The butyl glycol ether acetic ester; The 3-methoxypropanol; Methoxymethoxy ethanol; Diethylene glycol dimethyl ether; Diethylene glycol ether; Diethylene glycol dimethyl ether; Diethylene glycol diethyl ether; Propylene glycol methyl ether acetate; The propylene-glycol ethyl ether acetic ester; The N.N-N; 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).
Photosensitive composition of the present invention usually with this field oneself know the technology coating (as cutter be coated with, blade coating, bar are coated with, roller coat, extrusion, coiling rod are coated with etc.) on the version base.Be dissolved in appropriate solvent to photosensitive composition of the present invention or/and in the water, be made into coating fluid.
Use above-mentioned unmodified resol P01-P14, ammonia esterification modification hybrid phenol-formaldehyde resin P01M-P14M makes the positive heat-sensitive flat stamping version 1-flat stamping version 24 that the temperature-sensitive coating contains above-mentioned resin.
Positive heat-sensitive flat stamping version coating formula:
Sensitization liquid (each component by weight)
Resol (uses P01-P12, P01M-P12M) 71 respectively separately
Acidogenic agent (4,4'-dimethyl diphenyl salt compounded of iodine hexafluorophosphate, Shenyang sensitization research institute) 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
Pyoktanin blue (CI42535) 2
1-methoxyl group-2-propyl alcohol 900
The above-mentioned sensitization liquid of extrusion coated on above-mentioned version base descended dry 60 seconds at 120 ℃ then, obtained the coating dry weight of 1.8g/ ㎡.
Solvent resistance is investigated: above-mentioned plate sample is immersed in ethylene glycol butyl ether 80% aqueous solution 20 minutes and Virahol 50% aqueous solution 30 minutes respectively, cleans mensuration plate coating loss with the sponge wiping.
The plate imaging performance is investigated: Kodak's all-victorious 800 heat-sensitive plate-makings mechanism version, and Lekai China light produces the imaging of TPD-III developing liquid developing, and MASTER VIEW MV-CTP scouring machine is measured plate development flexibility and site performance.
Pressrun is investigated: machine on the above-mentioned plate sample is normally printed (Beiren's four looks four are driven high speed rotary press), investigate its pressrun.
The plate performance is seen attached list.
Application result by subordinate list shows; Contain ammonia esterification modification hybrid phenol-formaldehyde resin of the present invention and be used for temperature-sensitive flat stamping version; Can obviously strengthen the good solubility-resistence ability and the pressrun of temperature-sensitive version; This is that the flat stamping version has strong, the tough and tensile advantage of coating adhesion because strong polar ammonia ester bond exists in the ammonia esterification modification hybrid phenol-formaldehyde resin; Because of the linear polymerization hydridization second time, in resol, introduced the unique construction unit that contains the molten group of alkali again, improved the anti-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 flexibility and site performance all satisfy print request.
Claims (8)
1. ammonia esterification modification hybrid phenol-formaldehyde resin; It is characterized in that: it is through phenolic hydroxyl group ammonia esterification grafting vinyl monoisocyanates by linear phenolic resin; Carry out the hybrid phenol-formaldehyde resin that the second time, the radical linear polymerization obtained separately or with other vinyl monomer as high polymer monomer then, ammonia esterification modification hybrid phenol-formaldehyde resin weight-average molecular weight is 7500-150000; Softening temperature is 80-220 ℃.
2. ammonia esterification modification hybrid phenol-formaldehyde resin according to claim 1 is characterized in that: described linear phenolic resin is the linear condensation product of phenol, p-cresol, meta-cresol and composition thereof and formaldehyde, and molecular weight is 2500-14000.
3. ammonia esterification modification hybrid phenol-formaldehyde resin according to claim 1, it is characterized in that: described vinyl monoisocyanates has following general structure:
In the formula, R
1Be Wasserstoffatoms or methyl, R
2Be 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%.
4. ammonia esterification modification hybrid phenol-formaldehyde resin according to claim 1; It is characterized in that: described other vinyl monomer is to contain at least a in the vinyl monomer that sulfoamido or active maleimide and N-thereof replace the caustic solubility verivate in the structure, and its weight accounts for the 10-50% of copolymerization weight.
5. the preparation method of the described ammonia esterification modification of claim 1 hybrid phenol-formaldehyde resin; It is characterized in that: with linear phenolic resin in reaction solvent; Heated and stirred to linear phenolic resin dissolving back adds catalyzer under the nitrogen protection condition, drips the vinyl monoisocyanates then, under 40-120 ℃, reacts to ammonia esterification terminal point; 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; Carry out the hybrid phenol-formaldehyde resin that the second time, the radical linear polymerization obtained separately or with other vinyl monomer as high polymer monomer then.
6. the preparation method of ammonia esterification modification hybrid phenol-formaldehyde resin according to claim 5 is characterized in that: described linear phenolic resin is the linear condensation product of phenol, p-cresol, meta-cresol and composition thereof and formaldehyde, and molecular weight is 2500-14000.
7. the preparation method of ammonia esterification modification hybrid phenol-formaldehyde resin according to claim 5 is characterized in that: described vinyl monoisocyanates has following general structure:
In the formula, R
1Be Wasserstoffatoms or methyl, R
2Be 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%.
8. the preparation method of ammonia esterification modification hybrid phenol-formaldehyde resin according to claim 5; It is characterized in that: described other vinyl monomer is to contain at least a in the vinyl monomer that sulfoamido or active maleimide and N-thereof replace the caustic solubility verivate in the structure, and its weight accounts for the 10-50% of copolymerization weight.
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| CN114702633A (en) * | 2022-03-16 | 2022-07-05 | 陕西科技大学 | Modified resol and preparation method thereof |
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