A macrocyclic compound and its use, a processless thermal plate precursor comprising a macrocyclic compound and a processless thermal plate and use

Abstract

This invention provides a macrocyclic compound and its applications, a precursor for a processing-free thermal image containing the macrocyclic compound, and a processing-free thermal image and its applications. The macrocyclic compound is a product obtained by amine esterification of resorcinol calixarenes (CR) and isocyanate acrylate (ICA). Because the macrocyclic compound contains calixarenes, its macrocyclic cavity can encapsulate infrared absorbers and thermal initiators. Furthermore, the macrocyclic compound contains highly polar amine-activated double bonds, exhibiting high thermosensitive crosslinking activity, and can undergo crosslinking reactions with other components in the imaging layer to form a three-dimensional crosslinked structure, thereby solving the surface migration problem of infrared absorbers and thermal initiators in the imaging layer. In addition, the macrocyclic compound contains highly polar telechelic amine-activated allyl groups, exhibiting high thermosensitive crosslinking activity and abrasion resistance, effectively improving the imaging performance of the processing-free thermal image.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of advanced lithographic printing technology, and particularly relates to a macrocyclic compound, a processing-free thermal plate precursor containing the same, a processing-free thermal plate and application thereof. BACKGROUND

[0002] Modern printing widely adopts computer-to-plate technology (CTP), and common CTP plates are divided into photosensitive CTP plates and thermal CTP plates.

[0003] The most widely used one is a thermal CTP plate (thermal plate), which is a lithographic plate that can be imaged by infrared laser and can be operated in the open air, and has high imaging quality.

[0004] Environmental protection is an important issue facing the world, and green mountains and clear water are golden mountains and silver mountains. The traditional printing industry is a high-pollution industry that is not friendly to the environment, and the waste developer generated during the printing process causes great harm to the environment, so the printing industry all over the world is advocating the implementation of green printing technology.

[0005] Green printing technology refers to the use of environmentally friendly materials and process technology to reduce pollution during the printing process. The development of green and environmentally friendly printing plates is the top priority for the development of green printing.

[0006] Thermal plate technology is constantly progressing and developing, and thermal plate materials are also being updated, one of the directions of which is to explore processing-free thermal plates to reduce the use of developer during plate making.

[0007] There are many technical routes for processing-free thermal plates, which can be divided into thermal ablation technology, phase change technology and thermal melting technology, etc. Thermal ablation technology refers to the ablation of an oil-repellent coating by infrared laser energy to expose the hydrophilic surface of an aluminum plate to form a hydrophilic area; phase change technology refers to the hydrophilic-lipophilic conversion of a polymer caused by laser energy to achieve ink-water separation; thermal melting technology is the melting of thermoplastic polymer particles dispersed in a cross-linked hydrophilic layer by laser energy, which changes from hydrophilic to hydrophobic and lipophilic.

[0008] Processing-free thermal plates can be divided into two categories: (1) direct-to-press processing-free thermal plates. The plate material can be directly put on the machine after imaging, and developed and printed under the action of the dampening liquid of the printing machine; (2) low-chemical development processing-free thermal plates. The plate material is exposed and imaged on a plate making machine, and then washed with water to achieve development, and then put on the machine for printing.

[0009] The development of processing-free thermal plates, especially the development of processing-free thermal plate precursors, is a hot spot in the development of processing-free thermal plates in the world today. The precursor of the processing-free thermal plate refers to the precursor of the processing-free thermal plate, and generally refers to the necessary materials and technology required for the manufacture of the processing-free thermal plate.

[0010] Development of processless thermal plate precursor technology: Agfa patent EP 2006-5-24 06114475.4 discloses a kind of styrene-acrylic emulsion, which can be realized in the low chemical development of gum arabic aqueous solution; WO2013 / 032780 discloses a kind of lithographic printing plate precursor for on-press development; EP0980754 introduces decarboxylation to realize the technology of hydrophilic-hydrophobic conversion; WO94 / 23954 introduces hot melt to make microgel technology; US4004924 introduces a kind of mixture of thermoplastic hydrophobic particles and hydrophilic binder; EP 2006-5-24 06114475.4 introduces a kind of hot melt thermoplastic particles; US 2005-8-311 / 196,124 introduces a kind of one-dimensional linear structure hydrophilic binder; US 2006-7-27 11 / 494,235 introduces a kind of printing plate precursor containing hydrophilic group and esterified allyl group, etc.

[0011] At present, there are many technologies for processless thermal plate, one of the mainstream technologies is to use infrared absorber to make the heat energy of laser act on thermal initiator, and the thermal initiator triggers the chemical reaction of the thermal sensitive layer to realize laser imaging.

[0012] In the process of continuous progress of processless thermal plate technology, the technical personnel found that the infrared absorber and thermal initiator are prone to migration in the image layer, and the surface migration problem directly affects the initiation efficiency, causes insufficient deep layer initiation, uneven image color, non-realistic dot reproduction, and non-firm coating, etc.

[0013] In order to solve the surface migration problem of infrared absorber and thermal initiator in the imaging layer, improve the image quality, and further improve the performance of processless thermal plate, it is the purpose of the present application. SUMMARY

[0014] To solve the above problems, the present application provides a kind of macrocyclic compound and its application, the treatment-free thermal sensitive plate precursor and treatment-free thermal sensitive plate comprising macrocyclic compound and application, the macrocyclic compound is the product obtained by urethane reaction of resorcinol calixarene (CR) and isocyanate acrylate (ICA), since the macrocyclic compound contains calixarene, its macrocyclic cup cavity can have envelope infrared absorbent and thermal initiator, in addition, the macrocyclic compound contains strong polar urethane active double bond, has higher thermal sensitive crosslinking activity, can and other components in imaging layer occur crosslinking reaction to form three-dimensional crosslinking structure, thereby solving the surface migration problem of infrared absorbent and thermal initiator existing in imaging layer;In addition, the macrocyclic compound contains strong polar telechelic urethane allyl, has higher thermal sensitive crosslinking activity and wear resistance, can effectively improve the image performance of treatment-free thermal sensitive plate;The macrocyclic compound with infrared absorbent and thermal initiator enveloped in cup cavity forms three-dimensional reticular crosslinking structure after crosslinking imaging, effectively improves the overall mechanical structure of thermal sensitive layer, can effectively resist the erosion of UV ink, improves the printing resistance of thermal sensitive plate.

[0015] The object of the present application is achieved in the following way:

[0016] A kind of macrocyclic compound, characterized in that: macrocyclic compound is the product obtained by urethane reaction of resorcinol calixarene (CR) and isocyanate acrylate (ICA).

[0017] Wherein, isocyanate acrylate (ICA) has the following structure:

[0018]

[0019] R 1 For hydrogen atom or methyl, R 2 For ester group, aryl, ether group or covalent bond etc., r is the integer of 1-3.

[0020] Resorcinol calixarene (Calix [4] Resorcinarene, abbreviated as CR), it is prepared by cyclization of resorcinol and aldehyde under acidic conditions, and the aldehyde can be aliphatic aldehyde or aromatic aldehyde, and the reaction formula is as follows:

[0021]

[0022] Resorcinol calixarene is a kind of macrocyclic compound with cavity structure, and is an important supramolecular chemistry receptor, which can recognize guest molecules by means of hydrogen bond association, electrostatic adsorption, intermolecular van der Waals force and cavity effect, and can effectively recognize, adsorb and cage guest molecules. Each molecule of resorcinol calixarene contains 8 phenolic hydroxyl groups. In the present application, the resorcinol calixarene is modified, and the urethane double bond is grafted by urethane reaction between the phenolic hydroxyl groups of the resorcinol calixarene and the isocyanate groups. The macrocyclic compound after grafting has photosensitive and heat-sensitive activity.

[0023] Meanwhile, various organic compounds can be embedded in the cavity of the macrocyclic compound to form an inclusion complex, which can effectively adsorb the infrared absorber and the thermal initiator, thereby solving the surface migration problem of the infrared absorber and the thermal initiator in the imaging layer. Although the unmodified resorcinol calixarene can also adsorb the infrared absorber and the thermal initiator, the unmodified resorcinol calixarene is a single unit and cannot crosslink with other components in the imaging layer to form a three-dimensional crosslinked structure, so it cannot completely solve the surface migration problem of the infrared absorber and the thermal initiator in the imaging layer. However, the macrocyclic compound of the present application is prepared by urethane reaction of resorcinol calixarene (CR) and isocyanate acrylate (ICA), and a telechelic allyl group is formed on the resorcinol calixarene (CR) by the urethane bond. The cup cavity and the telechelic group can effectively wrap and entangle the infrared absorber and the thermal initiator. The macrocyclic compound contains a strong polar urethane active double bond, has high heat-sensitive crosslinking activity and wear resistance, and can effectively improve the performance of the processing-free thermal plate image. Meanwhile, the macrocyclic compound can form a three-dimensional network crosslinked structure after imaging, which can more effectively solve the surface migration problem of the infrared absorber and the thermal initiator in the imaging layer.

[0024] The resorcinol calixarene (CR) used for synthesizing the macrocyclic compound of the present application is preferably C-methyl resorcinol calix[4]arene.

[0025] The isocyanate acrylate (ICA) used for preparing the macrocyclic compound of the present application has the following structure:

[0026]

[0027] R 1 is a hydrogen atom or a methyl group, R 2 is an ester group, an aryl group, an ether group or a covalent bond, etc., and r is an integer of 1-3.

[0028] The isocyanate acrylate (ICA) is a high-function bridging intermediate, which contains both isocyanate groups and double bonds. Through urethane reaction, the isocyanate groups of the isocyanate acrylate can react with the phenolic hydroxyl groups of the resorcinol calixarene (CR) to form a high-activity telechelic urethane double bond on the resorcinol calixarene (CR).

[0029] Currently, only isocyanate acrylate (ICA) such as isocyanate acrylate ethyl ester (AOI, CAS No. 13641-96-8), isocyanate methacrylate ethyl ester (MOI, CAS No. 30674-80-7) and 2-(2-isocyanatoethoxy) methacrylate ethyl ester (MOI-EG, CAS No. 10723-60-9) have been successfully developed and industrialized in the world.

[0030] The isocyanate acrylate (ICA) used for preparing the macrocyclic compound of the present application is preferably isocyanate acrylate ethyl ester (AOI, CAS No. 13641-96-8) or isocyanate methacrylate ethyl ester (MOI, CAS No. 30674-80-7) or 2-(2-isocyanatoethoxy) methacrylate ethyl ester (MOI-EG, CAS No. 10723-60-9).

[0031] The macrocyclic compound of the present application is prepared by urethane reaction, and is a product obtained by urethane reaction of resorcinol calixarene (CR) and isocyanate acrylate (ICA). The urethane reaction is the reaction of the phenolic hydroxyl group of resorcinol calixarene (CR) and the isocyanate group of isocyanate acrylate (ICA). The molar number of the phenolic hydroxyl group contained in resorcinol calixarene (CR) is greater than or equal to the molar number of the isocyanate group contained in isocyanate acrylate (ICA). The reaction medium is preferably a solvent free of active hydrogen, such as dimethylformamide, dimethylacetamide, etc. The reaction catalyst is preferably an organic metal compound or an amine, such as stannous octoate, dibutyltin dilaurate, triethylamine, triethylenediamine, etc. The reaction temperature is preferably 50-100℃.

[0032] The application of the macrocyclic compound.

[0033] A processing-free thermal plate precursor, comprising a carrier, an imaging layer, the imaging layer comprising a hydrophilic thermal sensitive resin, a cross-linkable prepolymer, a macrocyclic compound, a thermal initiator and an infrared absorber; the macrocyclic compound is the macrocyclic compound described in the present application.

[0034] The processing-free thermal plate precursor described in the present application, the imaging layer comprises, by weight percentage, 40-80% of the total composition solid amount of the hydrophilic thermal sensitive resin, 10-50% of the total composition solid amount of the cross-linkable prepolymer, 5-30% of the total composition solid amount of the macrocyclic compound, 1-10% of the total composition solid amount of the thermal initiator and 1-10% of the total composition solid amount of the infrared absorber.

[0035] The processing-free thermal plate precursor of the present application can further have a protective layer on the imaging layer, which can prevent oxygen and protect the imaging layer. The protective layer can be made of a water-soluble polymer compound with good crystallinity, such as polyvinyl alcohol, polyvinylpyrrolidone, hydroxypropyl cellulose, gelatin, gum arabic, polyacrylic acid, and the like.

[0036] The hydrophilic thermal resin in the imaging layer is described as follows:

[0037] The processing-free thermal plate imaging layer requires a polymer resin, specifically, a functional-group-containing polymer film-forming resin. The hydrophilic thermal resin in the imaging layer of the present application is a functional film-forming resin. In addition to the film-forming property, which ensures that the imaging layer coating solution dries to form a film attached to the support, the hydrophilic thermal resin also has the special functions of hydrophilicity and thermal sensitivity.

[0038] The hydrophilic thermal resin in the processing-free thermal plate precursor of the present application is a branched polyolefin resin containing hydrophilic groups and epoxy groups. Further, the hydrophilic thermal resin in the processing-free thermal plate precursor of the present application is a polyolefin resin containing at least anionic side groups in the copolymer chain, allyl ether hydrophilic copolymer units, and epoxy acrylate copolymer units.

[0039] As the main resin in the imaging layer of the processing-free thermal plate, it must first have hydrophilicity. During laser imaging, the uncrosslinked part can be simply pre-cleaned with water or water containing gum, or cleaned under the action of dampening solution during on-press printing, to expose the hydrophilic plate base. The crosslinked imaging part after being heated by laser changes from hydrophilic to hydrophobic due to the change in polarity and solubility of the resin, as the hydrophilic resin and the prepolymer form a three-dimensional network structure. The best way to achieve water solubility of the resin is to directly select a vinyl monomer with a hydrophilic side group as the copolymer unit of the resin. The hydrophilic side groups include carboxyl, hydroxyl, phosphate, sulfonic acid, amino, amide, ether, and the like. The hydrophilic thermal resin of the present application contains at least anionic side group-containing allyl ether or urea side group-containing acrylamide hydrophilic copolymer units in the copolymer chain. The anionic side group-containing allyl ether or urea side group-containing acrylamide hydrophilic copolymer units endow the hydrophilic thermal resin with good self-emulsifying property, allowing the hydrophilic thermal resin to form nanometer thermoplastic particles, and the anionic side group-containing allyl ether and urea side group-containing acrylamide have higher polarity, which can resist the etching of solvents with lower polarity and have good solvent resistance, and can resist the etching of monomers in UV ink on the imaging layer.

[0040] The hydrophilic thermal resin of the present application contains at least anionic side group-containing allyl ether hydrophilic copolymer units in the copolymer chain. The anionic side group in the copolymer chain is preferably polyalkylene sulfonic acid and its salt or polyalkylene phosphoric acid and its salt, and the alkylene group is preferably ethylene group, which has the following structure:

[0041]

[0042] R1 is alkyl or alkoxy or aryl, R2 is H or CH3, and X is an acid or acid salt.

[0043] The hydrophilic heat-sensitive resin described in the present invention, the polyethenoic anionic side group contained in the copolymer chain is preferably polyethenoic sulfonic acid and its salt or polyethenoic phosphoric acid and its salt, i.e. X is sulfonic acid or phosphoric acid and their acid salts. Such compounds can be exemplified as follows (C1-C8), but are not limited thereto:

[0044] C1:

[0045]

[0046] C2:

[0047]

[0048] C3:

[0049]

[0050] C4:

[0051]

[0052] C5:

[0053]

[0054] C6:

[0055]

[0056] C7:

[0057]

[0058] C8:

[0059]

[0060] and salts of C8.

[0061] The urea-containing side group acrylamide copolymer unit can be exemplified as follows: acrylamidomethyl urea, methacrylamidomethyl urea, acrylamidodimethyl urea, N-acrylamido-N'-phenyl urea, N-acrylamido cyclohexyl urea, and the like.

[0062] In addition, as the main resin in the processing-free thermal plate imaging layer, the resin preferably contains a group sensitive to heat, which is helpful to thermal imaging. Such imaging groups can be double bonds capable of radical polymerization or epoxy groups capable of cationic polymerization, etc. The hydrophilic thermal resin of the present application contains a group sensitive to heat, and the epoxy group capable of cationic polymerization is selected as the photosensitive group, so that the resin structural unit contains an epoxy acrylate copolymerization unit, which can preferentially contain glycidyl methacrylate, 3,4-epoxy cyclohexyl methacrylate and other epoxy acrylate monomers, and further can preferentially contain epoxy acrylate monomers containing cyclohexyl groups, such as 3,4-epoxy cyclohexyl methacrylate. The cyclohexyl group has good rigidity, and the epoxy group on the cyclohexyl group has very high cationic polymerization activity.

[0063] Finally, as the main resin in the processing-free thermal plate imaging layer, the rigidity, ink affinity and other comprehensive properties of the resin also need to be considered. When the resin is in the form of nanometer particles as the adhesive of the processing-free thermal plate, the resin preferably contains a thermoplastic structural unit, which is helpful to laser heat film formation. The hydrophilic thermal resin of the present application preferably contains a styrene structural unit. It is well known that the styrene structural unit has good thermoplasticity and a high glass transition temperature, and the styrene copolymer as the adhesive of the processing-free thermal CTP plate has the advantages of being more easily heat-fused in the heated part, being more closely arranged between molecules, being more firm in the thermal image part, and being able to increase the printing resistance of the plate material. The thermoplastic structural unit can also be an acrylic copolymerization unit.

[0064] The hydrophilic thermal resin in the processing-free thermal plate imaging layer can be in the form of a solid body, a solution state or an emulsion state, etc.

[0065] The hydrophilic thermal resin described in the present application is preferably in the form of discrete particles, and the particle size is 50-200 nm.

[0066] During thermal imaging, the laser can cause the temperature of the thermoplastic polymer particles in the form of discrete particles to undergo a condensation reaction, and the exposed area changes from hydrophilic to hydrophobic and lipophilic.

[0067] The hydrophilic thermal resin described in the present application is synthesized by solution or emulsion copolymerization. The copolymerization can be random copolymerization or block copolymerization, and random copolymerization is preferred. The initiator for polymerization includes peroxides such as di-t-butyl peroxide and benzoyl peroxide, persulfates such as potassium persulfate and amine persulfate, and azo compounds such as azobisisobutyronitrile, etc. The copolymerization method is preferably emulsion polymerization.

[0068] The reaction solvent that can be used includes water, alcohols, ketones, esters, ethers and other solvents or mixtures thereof. The copolymerization temperature is preferably 40-100°C, and most preferably 60-90°C.

[0069] The hydrophilic heat-sensitive resin in the image layer is 40-80% by weight of the total solids content of the composition.

[0070] The cross-linkable prepolymer in the image layer is described below:

[0071] The cross-linkable prepolymer in the image layer can be a monomer capable of free radical polymerization or a monomer capable of cationic polymerization, etc. The monomer capable of free radical polymerization is generally an acrylic monomer containing a double bond, and the monomer capable of cationic polymerization is generally a monomer containing an epoxy group. The cross-linkable prepolymer in the image layer according to the present application is a multifunctional acrylic monomer or a multifunctional urethane acrylic monomer, where the meaning of multifunctional is that it contains multiple double bonds. The multifunctional acrylic monomers are, for example, 1,6-hexanediol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, trimethylolpropane triacrylate, hydroxypropyl glyceryl triacrylate, hydroxyethyl trimethylolpropane triacrylate, polyethylene glycol dimethacrylate, dipentaerythritol hexaacrylate, etc., and the multifunctional urethane acrylic monomers are products of condensation of isocyanate and multifunctional acrylate, such as a product of condensation of isocyanate with hydroxyethyl acrylate and pentaerythritol triacrylate, etc., or a product of condensation of isocyanate containing a double bond such as methacryloyloxy isocyanate and a polyhydroxy compound such as pentaerythritol.

[0072] The cross-linkable prepolymer in the image layer is 10-50% by weight of the total solids content of the composition.

[0073] The thermal initiator in the image layer is described below:

[0074] The plate material has the ability of radical polymerization imaging, and the thermal initiator is selected from onium salts, such as sulfonium salts, iodonium salts and the like. The onium salts simultaneously undergo homolysis and heterolysis under the action of heat, the onium salts homolysis generates free radicals, which initiate the radical polymerization of double bonds in the imaging layer, and the onium salts heterolysis generates cations, which initiate the cationic polymerization of epoxy bonds in the imaging layer, so that the processing-free thermal plate made of the precursor of the present application has the dual imaging ability of radical polymerization and cationic polymerization, the plate material has excellent imaging ability, and the curing of the influence layer can form a reticular crosslinked structure, which has very high wear resistance. Suitable onium salts include sulfonium salts, oxonolium salts, oxosulfonium salts, sulfoxonium salts, diazonium salts and halonium salts, such as iodonium salts and the like. Specific examples of suitable onium salts are: diphenyl iodonium chloride, diphenyl iodonium hexafluorophosphate, diphenyl iodonium hexafluoroantimonate, [4-[(2-hydroxytetradecyl-oxy]-phenyl]phenyl iodonium hexafluoroantimonate, triphenyl sulfonium onium tetrafluoroborate, triphenyl sulfonium onium octyl sulfate, 2-methoxy-4-amino phenyl diazonium hexafluorophosphate, phenoxy phenyl diazonium hexafluoroantimonate and the like. The thermal initiator of the present application is selected from iodonium salts or sulfonium salts which can simultaneously undergo homolysis and heterolysis. The thermal decomposition temperature thereof is 150-200℃. The thermal initiator accounts for 1-10% of the total weight of the thermal sensitive layer.

[0075] The infrared absorber in the imaging layer is described as follows:

[0076] The infrared absorber in the imaging layer of the present application mainly plays the role of energy transfer, and the heat of the infrared laser transfers the laser energy to the thermal initiator through the infrared absorber, the thermal initiator is cracked to generate active groups, the hydrophilic thermal sensitive resin and the crosslinkable prepolymer are three-dimensionally reticulated and polymerized, and thermal sensitive imaging is realized. The maximum absorption wavelength of the infrared absorber is in the range of 750-1100nm, and is selected from carbon black, azo dyes, triarylamine dyes, indolium dyes, oxonol dyes, cyanine dyes, phthalocyanine dyes, indocyanine dyes, phthalocyanine dyes, polythiophene dyes, pyrazoline azo dyes, oxazine dyes, naphthoquinone dyes, anthraquinone dyes, quinonimine dyes, methine dyes, porphyrin dyes and the like. In order to improve the plate making contrast, it is beneficial for the naked eye of the printing operator to detect the image defects of the plate, and at the same time, it is beneficial for the modern highly intelligent printing machine to realize automatic intelligent plate loading through the cross line image of the four corners of the plate material. The selected infrared absorber can be an infrared absorber with color changing function, which realizes the presentation of high contrast image through laser cracking. The infrared absorber in the imaging layer of the present application is preferably a cyanine dye with an absorption peak in the range of 750-850nm.

[0077] The infrared absorber in the imaging layer of the present application accounts for 1-10% of the total amount of the composition solid.

[0078] The carrier in the processing-free thermal plate precursor of the present application is described in detail as follows.

[0079] The imaging layer of the present application is coated on a support, which includes metal plate base such as steel base, copper base, aluminum base and the like.

[0080] The support of the present application is an aluminum plate base after electrolytic roughening and anodic oxidation.

[0081] The aluminum plate base is prepared by electrolytic roughening with an average roughness of 0.3-0.6um. The aluminum plate base contains more than 99% of aluminum, 0.1%-0.5% of iron, 0.03%-0.3% of silicon, 0.003%-0.03% of copper and 0.01%-0.1% of titanium. The electrolytic roughening electrolyte can be an aqueous solution of acid, alkali or salt. The aluminum plate is first chemically etched in an aqueous solution of 1%-30% of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate and the like at a temperature of 20-80°C for 5-250 seconds. Then the aluminum plate is neutralized in 10%-30% of nitric acid or sulfuric acid at a temperature of 20-70°C to remove the ash. The aluminum plate is electrolytically treated in the electrolyte of nitric acid or hydrochloric acid with a current density of 5-100 A / dm 2 for 10-300 seconds by using positive and negative alternating rectangular wave, square wave or sine wave at a temperature of 10-60°C. The aluminum plate base after electrolytic roughening and anodic oxidation is then subjected to anodic oxidation treatment. The anodic oxidation is usually carried out by sulfuric acid method using sulfuric acid with a concentration of 5-30% and a current density of 1-15 A / dm 2 at an oxidation temperature of 20-60°C for 5-250 seconds to form an oxide film with a thickness of 1-10 g / m 2 . Finally, the aluminum plate base is subjected to sealing treatment. The aluminum plate base after electrolytic roughening and anodic oxidation can be optionally subjected to sealing treatment. The sealing treatment can be carried out by various methods to seal 50-80% of the volume of the micropores of the oxide film. For example, the micropores of the oxide film of the aluminum plate after the above treatment are sealed by coating a polyvinyl phosphonic acid with a thickness of 3 mg / m 2 .

[0082] The present application provides a process for preparing a heat-sensitive plate precursor. The heat-sensitive plate precursor is prepared by coating an imaging layer on a support. The support includes metal plate base such as steel base, copper base, aluminum base and the like. The imaging layer of the present application is coated on a support, which includes metal plate base such as steel base, copper base, aluminum base and the like.

[0083] The processing-free thermal plate prepared by using the processing-free thermal plate precursor of the present application can also be added with some other necessary additives, such as solvents, room temperature thermal polymerization inhibitors, surfactants, layer colorants, etc. The solvents are mainly used to prepare the thermal composition into a thermal coating photosensitive solution, including alcohols, ketones, esters, ethers, amides, aromatic solvents, and ethylene dichloride, tetrahydrofuran, etc., which can be used in pure or mixture form; the room temperature thermal polymerization inhibitors are used to prevent the plate from polymerizing at room temperature, and to improve the room temperature stability of the plate. The thermal polymerization inhibitors include hydroquinone, nitrogen-oxygen free radical piperidinol, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butyl catechol, benzoquinone, 4,4'-thiobis-(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), and N-nitrosophenylhydroxylamine primary cerium salt, etc.; the layer colorants are added to increase the image density of the thermal plate after plate making, and to facilitate the visual inspection or image analysis measurement of the plate performance, which includes methyl violet, ethyl violet, crystal violet, crystal inner violet, Victoria blue, oil green, oil blue, oil yellow, rhodamine B, methyl violet orchid, malachite green, methylene blue, triazine, etc.; the coating also needs to be added with a surfactant, which can be selected from nonionic surfactants, amphoteric surfactants, silicon-containing surfactants, fluorine-containing surfactants, etc., such as betaine, glycerol stearate, sorbic brown oil ester, polysiloxane, polyfluoroalkyl ether, etc.

[0084] The processing-free thermal plate prepared by using the processing-free thermal plate precursor of the present application is generally coated by using the techniques known in the art, such as knife coating, blade coating, bar coating, roller coating, press coating, spray coating, etc.

[0085] The processing-free thermal plate prepared by using the processing-free thermal plate precursor of the present application is generally coated by using the techniques known in the art, such as knife coating, blade coating, bar coating, roller coating, press coating, spray coating, etc.

[0086] The macrocyclic compound provided by the present application is a product obtained by urethane reaction of resorcinol calixarene (CR) and isocyanate acrylate (ICA). Since the macrocyclic compound contains calixarene, the macrocyclic cup cavity thereof can envelop infrared absorbers and thermal initiators. In addition, the macrocyclic compound contains a strong polar urethane active double bond, has high thermal sensitive crosslinking activity, and can crosslink with other components in the imaging layer to form a three-dimensional crosslinked structure, thereby solving the surface migration problem of the infrared absorbers and thermal initiators existing in the imaging layer. In addition, the macrocyclic compound containing a strong polar telechelic urethane allyl group has high thermal sensitive crosslinking activity and wear resistance, which can effectively improve the image performance of the processing-free thermal plate. The macrocyclic compound enveloping infrared absorbers and thermal initiators in the cup cavity forms a three-dimensional network crosslinked structure after crosslinking imaging, effectively improves the overall mechanical structure of the thermal sensitive layer, can effectively resist the erosion of UV ink, and improves the printing resistance of the thermal plate. DETAILED DESCRIPTION

[0087] The present application will be described in detail below in conjunction with specific examples. It is necessary to point out here that the examples are only used to further illustrate the present application and cannot be understood as limiting the protection scope of the present application. Those skilled in the art can make some non-essential improvements and adjustments according to the content of the present application.

[0088] The following are synthesis examples of the present application, but the present application is not limited to the following examples.

[0089] First part: synthesis example of macrocyclic compound (code: M-CR)

[0090] The macrocyclic compound (code: M-CR) of the present application is synthesized by Huakehua Optical, and the following is the basic synthesis route:

[0091] The main raw materials can be obtained from the following companies:

[0092] C-methyl resorcinol calix[4]arene (CAS registration number: 65338-98-9): from Shanghai Kaijin Chemical Co., Ltd.; isocyanate acrylate ethyl ester (AOI, CAS registration number: 13641-96-8), isocyanate methyl acrylate ethyl ester (MOI, CAS registration number: 30674-80-7), 2-(2-isocyanatoethoxy) methyl acrylate (MOI-EG, CAS registration number: 107023-60-9): Japan Showa Denko K.K.; dibutyltin dilaurate, triethylenediamine: Tianjin Chemical Reagent No. 2 Factory; dimethylformamide (DMF) and dimethylacetamide (DMAC): Shanghai Union Carbide Chemical.

[0093] Synthesis of M-CR1:

[0094] In a 500 ml four-necked flask with temperature-controlled heating, mechanical stirring, condensation reflux and nitrogen protection device, 54.46 g of C-methyl resorcinol calix[4] arene, 14.11 g of isocyanate acrylate ethyl (AOI), 150 g of dimethyl formamide (DMF), and 0.1 g of dibutyl tin dilaurate were added, and the reaction was completed after stirring at 50°C for 3 hours, and then the target product M-CR1 was obtained. The reaction solution containing the target product can be directly used.

[0095] Synthesis of M-CR2:

[0096] In a 500 ml four-necked flask with temperature-controlled heating, mechanical stirring, condensation reflux and nitrogen protection device, 54.46 g of C-methyl resorcinol calix[4] arene, 112.90 g of isocyanate acrylate ethyl (AOI), 150 g of dimethyl formamide (DMF), and 0.8 g of dibutyl tin dilaurate were added, and the reaction was completed after stirring at 60°C for 3 hours, and then the target product M-CR2 was obtained. The reaction solution containing the target product can be directly used.

[0097] Synthesis of M-CR3:

[0098] In a 500 ml four-necked flask with temperature-controlled heating, mechanical stirring, condensation reflux and nitrogen protection device, 54.46 g of C-methyl resorcinol calix[4] arene, 56.45 g of isocyanate acrylate ethyl (AOI), dimethyl acetamide (DMAC), and 0.4 g of triethylene diamine were added, and the reaction was completed after stirring at 70°C for 3 hours, and then the target product M-CR3 was obtained. The reaction solution containing the target product can be directly used.

[0099] Synthesis of M-CR4:

[0100] In a 500 ml four-necked flask with temperature-controlled heating, mechanical stirring, condensation reflux and nitrogen protection device, 54.46 g of C-methyl resorcinol calix[4] arene, 46.55 g of isocyanate methyl acrylate ethyl (MOI), 150 g of dimethyl formamide (DMF), and 0.3 g of dibutyl tin dilaurate were added, and the reaction was completed after stirring at 80°C for 3 hours, and then the target product M-CR4 was obtained. The reaction solution containing the target product can be directly used.

[0101] Synthesis of M-CR5:

[0102] In a 500 ml four-necked flask with temperature-controlled heating, mechanical stirring, condensation reflux and nitrogen protection device, 54.46 g of C-methyl resorcinol calix[4] arene, 3.10 g of isocyanate methyl methacrylate (MOI), dimethylacetamide (DMAC), and 0.7 g of triethylene diamine were added, and the reaction was completed after stirring at 90°C for 1.5 hours, and then the target product M-CR5 was obtained. The reaction solution containing the target product can be directly used.

[0103] Synthesis of M-CR6:

[0104] In a 500 ml four-necked flask with temperature-controlled heating, mechanical stirring, condensation reflux and nitrogen protection device, 54.46 g of C-methyl resorcinol calix[4] arene, 39.84 g of 2-(2-isocyanatoethoxy) methyl methacrylate MOI-EG, 150 g of dimethylformamide (DMF), and 0.2 g of dibutyl tin dilaurate were added, and the reaction was completed after stirring at 75°C for 3 hours, and then the target product M-CR6 was obtained. The reaction solution containing the target product can be directly used.

[0105] Synthesis of M-CR7:

[0106] In a 500 ml four-necked flask with temperature-controlled heating, mechanical stirring, condensation reflux and nitrogen protection device, 54.46 g of C-methyl resorcinol calix[4] arene, 99.60 g of 2-(2-isocyanatoethoxy) methyl methacrylate MOI-EG, dimethylacetamide (DMAC), and 0.5 g of dibutyl tin dilaurate were added, and the reaction was completed after stirring at 100°C for 1 hour, and then the target product M-CR7 was obtained. The reaction solution containing the target product can be directly used.

[0107] Synthesis of M-CR8:

[0108] In a 500 ml four-necked flask with temperature-controlled heating, mechanical stirring, condensation reflux and nitrogen protection device, 54.46 g of C-methyl resorcinol calix[4] arene, 119.52 g of 2-(2-isocyanatoethoxy) methyl methacrylate MOI-EG, dimethylacetamide (DMAC), and 0.6 g of triethylene diamine were added, and the reaction was completed after stirring at 100°C for 0.5 hours, and then the target product M-CR8 was obtained. The reaction solution containing the target product can be directly used.

[0109] Second part: synthesis examples of hydrophilic thermosensitive resins (Nos. A1-A14).

[0110] Main raw materials can be obtained from the following companies: styrene St, methyl methacrylate MMA, hydroxyethyl methacrylate HEMA, acrylonitrile AN, acrylamide methylene urea, methacrylamide methylene urea, isopropyl alcohol from Shanghai Bailingwei Technology; Example compounds C1 (allyl ether polyethylene glycol sulfonate), C7 (allyl ether nonylphenol propyl alcohol polyethoxy ammonium sulfate), C8 (allyl ether polypropylene glycol phosphate) (the number average of the three example compounds polyethoxy addition is 10) from Japan Aidi Company; 3,4-epoxycyclohexyl methacrylate CMA from Mitsubishi Rayon Chemical Co., Ltd. of Japan; methyl ethyl ketone MEK: Lanzhou Petrochemical, azobis isobutyronitrile AIBN: Tianjin Fuchan Chemical Reagent; methacrylamide ethyl ethylene urea (MAEEU) from Shanghai Sangjing Chemical Technology Co., Ltd.

[0111] Hydrophilic heat-sensitive resin A1:

[0112] In a 500 ml beaker, 100 g of deionized water, 70 g (70 wt%) of styrene St, 10 g of C1 (10 wt%), 10 g (10 wt%) of methacrylamide methylene urea, 10 g (10 wt%) of 3,4-epoxycyclohexyl methacrylate, 1 g of azobis isobutyronitrile were emulsified under high-speed shearing at 800 rpm to prepare a pre-emulsion.

[0113] In a 500 ml four-necked flask with temperature control heating, mechanical stirring, condensation reflux and nitrogen protection device, 200 g of deionized water was added, and the temperature was raised to 80°C. The pre-emulsion mixture was added dropwise for 60 minutes, and then reacted at 80°C for 8 hours. 0.51 g of azobis isobutyronitrile was added, and the reaction was continued for 8 hours. After cooling, the reaction was stopped. The particle size was measured to be 105 nm. The reaction solution was used directly according to the solid content.

[0114] Hydrophilic heat-sensitive resin A2:

[0115] In a 500 ml beaker, 100 g of deionized water, 70 g (70 wt%) of styrene St, 10 g of C7 (10 wt%), 10 g (10 wt%) of methacrylamide methylene urea, 10 g (10 wt%) of 3,4-epoxycyclohexyl methacrylate, 1 g of azobis isobutyronitrile were emulsified under high-speed shearing at 800 rpm to prepare a pre-emulsion.

[0116] In a 500 ml four-necked flask with temperature control heating, mechanical stirring, condensation reflux and nitrogen protection device, 200 g of deionized water was added, and the temperature was raised to 80°C. The pre-emulsion mixture was added dropwise for 60 minutes, and then reacted at 80°C for 8 hours. 0.51 g of azobis isobutyronitrile was added, and the reaction was continued for 8 hours. After cooling, the reaction was stopped. The particle size was measured to be 138 nm. The reaction solution was used directly according to the solid content.

[0117] Hydrophilic heat-sensitive resin A3:

[0118] In a 500 ml beaker, 100 g of deionized water, 50 g (50 wt%) of styrene St, 10 g (10 wt%) of methyl methacrylate MMA, 15 g of C7 (15 wt%), 10 g (10 wt%) of acrylamide methylene urea, 15 g (15 wt%) of 3,4-epoxycyclohexyl methacrylate, 1 g of azobisisobutyronitrile were emulsified under the action of an ultrasonic emulsifier to prepare a pre-emulsion.

[0119] In a 500 ml four-necked flask with temperature-controlled heating, mechanical stirring, condensation reflux and nitrogen protection device, 200 g of deionized water was added, and the temperature was raised to 80°C to start dropping the following pre-emulsion mixture. The dropping time was 60 minutes, and then the reaction was carried out at 80°C for 8 hours. 0.51 g of azobisisobutyronitrile was added, and the reaction was continued for 8 hours. Then the reaction was terminated by cooling. The particle size was 125 nm. The reaction raw liquid was used directly according to the solid content.

[0120] Hydrophilic heat-sensitive resin A4:

[0121] In a 500 ml beaker, 350 g of deionized water, 50 g (50 wt%) of styrene St, 10 g (10 wt%) of hydroxyethyl methacrylate HEMA, 10 g of C7 (10 wt%), 10 g (10 wt%) of acrylamide methylene urea, 20 g (20 wt%) of 3,4-epoxycyclohexyl methacrylate, 1 g of azobisisobutyronitrile were added, and then the reaction was carried out at 80°C for 8 hours. 0.51 g of azobisisobutyronitrile was added, and the reaction was continued for 8 hours. Then the reaction was terminated by cooling. The particle size was 50 nm. The reaction raw liquid was used directly according to the solid content.

[0122] Hydrophilic heat-sensitive resin A5:

[0123] In a 500 ml beaker, 100 g of deionized water, 20 g of C7 (20 wt%), 20 g (20 wt%) of acrylamide methylene urea, 60 g (60 wt%) of 3,4-epoxycyclohexyl methacrylate, 1 g of azobisisobutyronitrile were emulsified under high-speed shearing at 800 rpm to prepare a pre-emulsion.

[0124] In a 500 ml four-necked flask with temperature-controlled heating, mechanical stirring, condensation reflux and nitrogen protection device, 200 g of deionized water was added, and the temperature was raised to 80°C to start dropping the following pre-emulsion mixture. The dropping time was 60 minutes, and then the reaction was carried out at 80°C for 8 hours. 0.51 g of azobisisobutyronitrile was added, and the reaction was continued for 8 hours. Then the reaction was terminated by cooling. The particle size was 165 nm. The reaction raw liquid was used directly according to the solid content.

[0125] Hydrophilic heat-sensitive resin A6:

[0126] In a 500 ml beaker, 100 g of deionized water, 40 g (40 wt%) of styrene St, 15 g C7 (15 wt%), 15 g (15 wt%) of acrylamidemethylene urea, 30 g (30 wt%) of 3,4-epoxycyclohexyl methacrylate, 1 g of azobisisobutyronitrile were added to prepare a pre-emulsion under high-speed shearing at 800 rpm.

[0127] In a 500 ml four-necked flask with temperature-controlled heating, mechanical stirring, condensation reflux and nitrogen protection device, 200 g of deionized water was added, and the temperature was raised to 80°C to start dropping the following pre-emulsion mixture. The dropping time was 60 minutes, and then the reaction was carried out at 80°C for 8 hours. 0.51 g of azobisisobutyronitrile was added as a supplement to continue the reaction for 8 hours, and then the reaction was terminated by cooling. The particle size was measured to be 185 nm. The reaction stock solution was used directly according to the solid content.

[0128] Hydrophilic thermosensitive resin A7:

[0129] In a 500 ml beaker, 100 g of deionized water, 20 g (70 wt%) of styrene St, 50 g (50 wt%) of acrylonitrile AN, 10 g C7 (10 wt%), 10 g (10 wt%) of acrylamidemethylene urea, 10 g (10 wt%) of 3,4-epoxycyclohexyl methacrylate, 1 g of azobisisobutyronitrile were added to prepare a pre-emulsion under high-speed shearing at 800 rpm.

[0130] In a 500 ml four-necked flask with temperature-controlled heating, mechanical stirring, condensation reflux and nitrogen protection device, 200 g of deionized water was added, and the temperature was raised to 80°C to start dropping the following pre-emulsion mixture. The dropping time was 60 minutes, and then the reaction was carried out at 80°C for 8 hours. 0.51 g of azobisisobutyronitrile was added as a supplement to continue the reaction for 8 hours, and then the reaction was terminated by cooling. The particle size was measured to be 200 nm. The reaction stock solution was used directly according to the solid content.

[0131] Hydrophilic thermosensitive resin A8:

[0132] In a 500 ml beaker, 100 g of deionized water, 70 g (70 wt%) of styrene St, 10 g C8 (10 wt%), 10 g (10 wt%) of acrylamidemethylene urea, 10 g (10 wt%) of 3,4-epoxycyclohexyl methacrylate, 1 g of azobisisobutyronitrile were added to prepare a pre-emulsion under high-speed shearing at 800 rpm.

[0133] 200g of deionized water was added to a 500ml four-necked flask equipped with a temperature-controlled heater, mechanical stirrer, reflux condenser, and nitrogen protection device. The temperature was raised to 80℃, and the following pre-emulsified mixture was added dropwise over 60 minutes. The reaction was then carried out at 80℃ for 8 hours. 0.51g of azobisisobutyronitrile was added, and the reaction continued for another 8 hours. The temperature was then lowered to stop the reaction. The particle size was measured to be 173nm. The stock solution was used directly based on its solids content.

[0134] Hydrophilic thermosensitive resin A9:

[0135] Add 100g deionized water, 70g (70 wt%) styrene (St), 10g C8 (10 wt%), 10g (10 wt%) acrylamide methylene urea, 10g (10 wt%) 3,4-epoxycyclohexyl methacrylate, and 1g azobisisobutyronitrile to a 500ml beaker, and emulsify under high-speed shear at 800 rpm to prepare a pre-emulsion.

[0136] Add 200g of deionized water to a 500ml four-necked flask equipped with a temperature-controlled heater, mechanical stirrer, reflux condenser, and nitrogen protection device. Heat to 80℃ and begin dropwise addition of the pre-emulsified mixture described above over 60 minutes. Then react at 80℃ for 8 hours. Add 0.51g of azobisisobutyronitrile and continue the reaction for another 8 hours. Adjust the pH to neutral with ammonia water, then cool to stop the reaction. The particle size was measured to be 180nm. The stock solution was used directly based on its solids content.

[0137] Hydrophilic thermosensitive resin A10:

[0138] Add 100g deionized water, 50g (50% by weight) styrene (St), 10g (10% by weight) methyl methacrylate (MMA), 15g C8 (15% by weight), 10g (10% by weight) acrylamide methylene urea, 15g (15% by weight) 3,4-epoxycyclohexyl methacrylate, and 1g azobisisobutyronitrile to a 500ml beaker and emulsify under the action of an ultrasonic emulsifier to prepare a pre-emulsion.

[0139] Add 200g of deionized water to a 500ml four-necked flask equipped with a temperature-controlled heater, mechanical stirrer, reflux condenser, and nitrogen protection device. Heat to 80℃ and begin dropwise addition of the pre-emulsified mixture described above over 60 minutes. Then react at 80℃ for 8 hours. Add 0.51g of azobisisobutyronitrile and continue the reaction for another 8 hours. Adjust the pH to neutral with NaOH, then cool to stop the reaction. The particle size was measured to be 105nm. The stock solution was used directly based on its solids content.

[0140] Hydrophilic thermosensitive resin A11:

[0141] In a 500 ml beaker, add 330 g deionized water, 50 g (50 wt%) styrene (St), 10 g (10 wt%) hydroxyethyl methacrylate (HEMA), 10 g (10 wt%) C8, 10 g (10 wt%) acrylamide methylene urea, 20 g (20 wt%) 3,4-epoxycyclohexyl methacrylate, and 1 g azobisisobutyronitrile (AIBN). React at 80 °C for 8 hours. Add 0.51 g AIBN and continue the reaction for another 8 hours. Adjust the pH to neutral with ammonia, then cool to stop the reaction. The particle size was measured to be 75 nm. The stock solution was used directly based on its solids content.

[0142] Hydrophilic thermosensitive resin A12:

[0143] Add 100g deionized water, 20g C8 (20 wt%), 20g (20 wt%) methacrylamide ethyl ethylene urea (MAEEU), 60g (60 wt%) 3,4-epoxycyclohexyl methacrylic acid, and 1g azobisisobutyronitrile to a 500ml beaker and emulsify under high-speed shear at 800 rpm to prepare a pre-emulsion.

[0144] Add 200g of deionized water to a 500ml four-necked flask equipped with a temperature-controlled heater, mechanical stirrer, reflux condenser, and nitrogen protection device. Heat to 80℃ and begin dropwise addition of the pre-emulsified mixture described above over 60 minutes. Then react at 80℃ for 8 hours. Add 0.51g of azobisisobutyronitrile and continue the reaction for another 8 hours. Adjust the pH to neutral with ammonia water, then cool to stop the reaction. The particle size was measured to be 95nm. The stock solution was used directly based on its solids content.

[0145] Hydrophilic thermosensitive resin A13:

[0146] Add 100g deionized water, 40g (40 wt%) styrene (St), 15g C8 (15 wt%), 15g (15 wt%) acrylamide methylene urea, 30g (30 wt%) 3,4-epoxycyclohexyl methacrylate, and 1g azobisisobutyronitrile to a 500ml beaker, and emulsify under high-speed shear at 800 rpm to prepare a pre-emulsion.

[0147] Add 200g of deionized water to a 500ml four-necked flask equipped with a temperature-controlled heater, mechanical stirrer, reflux condenser, and nitrogen protection device. Heat to 80℃ and begin dropwise addition of the pre-emulsified mixture described above over 60 minutes. Then react at 80℃ for 8 hours. Add 0.51g of azobisisobutyronitrile and continue the reaction for another 8 hours. Adjust the pH to neutral with ammonia water, then cool to stop the reaction. The particle size was measured to be 120nm. The stock solution was used directly based on its solids content.

[0148] Hydrophilic thermosensitive resin A14:

[0149] Add 100g deionized water, 20g (70 wt%) styrene (St), 50g (50 wt%) acrylonitrile (AN), 10g C8 (10 wt%), 10g (10 wt%) acrylamide methylene urea, 10g (10 wt%) 3,4-epoxycyclohexyl methacrylate, and 1g azobisisobutyronitrile to a 500ml beaker, and emulsify under high-speed shear at 800 rpm to prepare a pre-emulsion.

[0150] Add 200g of deionized water to a 500ml four-necked flask equipped with a temperature-controlled heater, mechanical stirrer, reflux condenser, and nitrogen protection device. Heat to 80℃ and begin dropwise addition of the pre-emulsified mixture described above over 60 minutes. Then react at 80℃ for 8 hours. Add 0.51g of azobisisobutyronitrile and continue the reaction for another 8 hours. Adjust the pH to neutral with ammonia water, then cool to stop the reaction. The particle size was measured to be 135nm. The stock solution was used directly based on its solids content.

[0151] According to Agfa patent EP 2006-5-24 06114475.4, Agfa polymer F is synthesized. The polymer does not contain hydrophilic groups, and the polymer structure is as follows:

[0152]

[0153] Basic procedure: In a 1000 ml four-necked flask equipped with temperature-controlled heating, mechanical stirring, reflux condenser, and nitrogen protection, add 75 g of deionized water, 250 g of isopropanol, and 5 g of sodium dodecyl sulfate. At 80 °C, add 60 g (60 wt%) of St (styrene), 40 g (40 wt%) of AN (acrylonitrile), and 0.7 g of AIBN (azobisisobutyronitrile) dropwise over 0.5 hours. After reacting for another 7.5 hours, add 0.3 g of AIBN (azobisisobutyronitrile) and continue reacting for another 12 hours to complete the reaction.

[0154] According to Kodak patent US 2005-8-3 11 / 196, Kodak polymer K was synthesized. The polymer contains hydrophilic polyether groups but does not contain epoxy groups. The polymer structure is as follows:

[0155]

[0156] Basic procedure: Add 75g of deionized water and 250g of n-propanol to a 1000ml four-necked flask equipped with temperature-controlled heating, mechanical stirring, reflux condenser, and nitrogen protection. At 80℃, add 20g (20 wt%) St (styrene), 70g (70 wt%) AN (acrylonitrile), 10g (10 wt%) PEGMA (polyethoxymethyl methacrylate), and AIBN (azobisisobutyronitrile) dropwise over 0.5 hours. After reacting for another 7.5 hours, add 0.3g of AIBN (azobisisobutyronitrile) and continue reacting for another 12 hours.

[0157] Example 1

[0158] Preparation of the substrate: A1050 rolled aluminum plate with a purity of 99.5% and a thickness of 0.3 mm was immersed in a 5% sodium hydroxide aqueous solution at 70°C for 20 seconds. After rinsing with running water, it was immediately neutralized with a 1% nitric acid aqueous solution. Then, it was immersed in a 1% hydrochloric acid aqueous solution at 40°C with a sinusoidal alternating current of 50 A / dm². 2 The surface was roughened by electrolysis at a current density of 16 seconds, followed by neutralization with a 5% sodium hydroxide aqueous solution at 40°C for 10 seconds, and then washed with water. Finally, it was roughened by electrolysis with a 20% sulfuric acid aqueous solution at 30°C at 15 A / dm³. 2 The current density was adjusted, and anodizing was performed for 20 seconds, followed by water washing. The substrate was then sealed with a 5% sodium silicate aqueous solution at 80℃ for 18 seconds, washed with water, and dried. The resulting substrate had an average centerline thickness of 0.5 μm and an oxide film weight of 3.0 g / dm². 2 .

[0159] Imaging layer materials: Infrared absorbers meeting the requirements of this invention can be obtained from Dye Chemical or Merck. In the example, the infrared absorber (IR820) is Merck's Sigma-Adrich 543365, chemical name: 2-[2-[2-chloro-3-[[1,3-dihydro-1,1-dimethyl-3-(4-sulfonate butyl)-2H-benzo[e]indol-2-ethylene]-1-cyclohexen-1-yl]-vinyl]-1,1-dimethyl-3-(4-sulfonate butyl)-1H-benzo[e]indolium hydroxide inner salt; Multifunctional acrylate: SR399 is dipentaerythritol pentaacrylate from Sartoma; Multifunctional polyurethane acrylate: PU100 is polyurethane acrylate. It is a condensation polymer of Covestro Desmodurn 100, hydroxyethyl acrylate, and pentaerythritol triacrylate, obtained from Shenyang Chemical Research Institute; thermal initiators: diphenyliodonium tetrafluoroborate (code: B1), 4,4-di-tert-butyldiphenyliodonium hexafluorophosphate (code: B2), triphenylthionium tetrafluoroborate (code: B3), and methyl diphenylthionium tetrafluoroborate (code: B4) are from Bailingwei Company; surfactant BYK306 is from BYK Company; 1-methoxy-2-propanol is from Union Carbide Chemicals; polyvinyl alcohol PVA-205 is from Kuraray Corporation of Japan; polyvinylpyrrolidone PVPK30 is from BASF of Germany; and emulsifier OP-10 is from Hamm of Germany.

[0160] Imaging layer materials (specific materials and quantities are shown in Table 2):

[0161] Hydrophilic thermosensitive resin 80

[0162] Crosslinkable prepolymer 13

[0163] Macrocyclic compound M-CR1 5

[0164] Thermal initiator 1

[0165] Infrared absorber (IR820) 1

[0166] The above raw materials were mixed with 0.5g of surfactant BYK306 and 700g of 1-methoxy-2-propanol to prepare an imaging layer coating solution. This coating solution was then applied to the hydrophilically treated substrate by extrusion and drying at 100°C for 60 seconds. A solution of 15 mg / dm³ was obtained. 2 The dry weight of the coating.

[0167] Alternatively, a protective layer can be extruded and coated onto the imaging layer, followed by drying at 110°C for 60 seconds. This yields a solution of 10 mg / dm³. 2 The dry weight of the coating.

[0168] Protective layer formulation:

[0169] Polyvinyl alcohol (PVA-205) (Kuraray, Japan) 17g

[0170] Polyvinylpyrrolidone (PVPK30) (BASF, Germany) 3g

[0171] Emulsifier OP-10 (Häm, Germany) 0.45g

[0172] 480g of deionized water

[0173] Different thermal plates were prepared using the same process described above: the base, protective layer, solvent, and other necessary additives remained unchanged. The imaging layer formulation was modified according to the data given in Table 1 to produce Examples 1-22. Only Example 1 had a protective layer coated, while the other examples did not. The performance of the thermal plates in these examples is listed in Table 2 below.

[0174] Testing and analysis of printing plates:

[0175] Initial: refers to the moment when the printing plate is first manufactured;

[0176] Forced aging: Simulating the state of natural storage in a forced manner;

[0177] 1. Initial Sensitivity: Sensitivity is characterized by the laser energy required for imaging. The lower the initiation efficiency of freshly produced plates, the higher the energy required for laser imaging. All the freshly produced plates were placed on a Kodak Allwinner thermal CTP plate-making machine at 5 mJ / cm². 2 The progressive amount is between 80-200 mJ / cm 2Exposure was performed within the energy range of the plate, and the initial sensitivity of the plate was measured according to the Pantone LIVE color digital workflow. The performance is listed in Table 2 below.

[0178] 2. Initial Dot Quality: Dot quality is characterized by whether 1%-99% of the dots can be reproduced after laser imaging. For example, 1-99% means that dots from 1% to 99% can be reproduced, which is the optimal value. 2-98% means that only 2-98% of the dots can be reproduced, and 1% and 99% of the dots cannot be reproduced, which is slightly worse, and so on. The lower the induction efficiency of the newly produced plate, the less likely it is to completely reproduce 1-100% of the dots. All the above plates were exposed on a Kodak Allwinner thermal CTP plate-making machine with optimal sensitivity and energy, and the initial dot reproduction value of the image was measured according to the Pantone LIVE color digital workflow. Their performance is listed in Table 2 below.

[0179] 3. Forced Aging Sensitivity: Forced aging simulates the changes of thermal plates under natural storage conditions within their shelf life. All the aforementioned plates are placed in a standard thermal plate product packaging box and subjected to forced aging for 5 days in an aging chamber at 40℃ and 80% humidity. Then, on a Kodak Allwinner thermal CTP plate-making machine, they are subjected to aging at 5 mJ / cm². 2 The progressive amount is between 80-200 mJ / cm 2 Exposure was performed within the energy range of the plate, and the sensitivity of the plate was measured according to the Pantone LIVE color digital workflow. The performance is listed in Table 2 below.

[0180] 4. Forced aging dot quality: Place all the above plates in a standard thermal plate product packaging box and force age them for 5 days in an aging chamber at 40℃ and 80% humidity. Then expose them on a Kodak Allwinner thermal CTP plate-making machine with the optimal sensitivity energy and measure their image dot reproduction value according to the Pantone LIVE color digital workflow. The performance is listed in Table 2 below.

[0181] 5. Migration Rating: All the above-mentioned plates are placed in a standard thermal plate product packaging box and forced to age for 7 days in an aging chamber at 40℃ and 80% humidity. After that, the thermal initiator migrates to the surface of the plate, and the appearance will be different compared with the freshly made thermal plate. The appearance quality of the thermal plate is analyzed and rated using an X.rite eXact scanning spectrophotometer according to the Pantone LIVE color digital workflow to obtain the migration value. The score is 10 points, from 1 to 10 points, with 10 points being the worst and 1 point being the best.

[0182] 6. Print Durability: If the iodine salt initiation efficiency is low and the imaging layer is not fully cured, the printing plate's durability will be reduced. Furthermore, if the iodine salt undergoes surface migration within the imaging layer, and laser exposure also produces small molecules that break down the imaging layer structure, this will significantly reduce the printing plate's durability. The total number of normal prints produced using the thermal plate was tested using a Heidelberg-XL754C printing press; the performance is listed in Table 2 below.

[0183] The test results in Table 2 show that, compared with the comparative example of treatment-free printing plates, the thermal plate manufactured using the treatment-free thermal plate precursor of this invention exhibits superior imaging performance, stability, and printing durability. This is because the treatment-free thermal plate precursor contains a macrocyclic compound whose cup cavity can effectively adsorb and encapsulate infrared absorbers and thermal initiators. Furthermore, the macrocyclic compound contains highly polar urethane-based active double bonds, exhibiting high thermosensitive crosslinking activity. It can undergo crosslinking reactions with other components in the imaging layer to form a three-dimensional crosslinked structure, thereby solving the surface migration problem of infrared absorbers and thermal initiators in the imaging layer. Additionally, the macrocyclic compound contains highly polar telechelic urethane-based allyl groups, possessing high thermosensitive crosslinking activity and abrasion resistance. After crosslinking and imaging, it can form a three-dimensional network crosslinked structure, effectively improving the overall mechanical properties of the thermal layer and effectively resisting UV ink erosion, thus enhancing the printing durability of the thermal plate. This thermal plate uses a precursor containing a specially structured hydrophilic thermosensitive resin, possessing chemical-free thermosensitive imaging capabilities, making it a green and environmentally friendly thermal plate material.

[0184] Table 1. Material Feed Table for Imaging Layer of Example Plate (Unit: grams)

[0185]

[0186] Table 2 Application Performance Table of Plates

[0187]

[0188] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. It should be noted that for those skilled in the art and any person skilled in the art, any equivalent substitutions or changes made to the technical solution and inventive concept of the present invention without departing from the overall concept of the present invention, as well as any changes and improvements made, should also be considered within the scope of protection of the present invention.

Claims

1. A processless thermal plate precursor comprising a support and an imaging layer, characterized in that: The imaging layer comprises a hydrophilic heat-sensitive resin, a cross-linkable prepolymer, a macrocyclic compound, a thermal initiator and an infrared absorber, wherein the hydrophilic heat-sensitive resin accounts for 40-80% of the total solid content of the composition, the cross-linkable prepolymer accounts for 10-50% of the total solid content of the composition, the macrocyclic compound accounts for 5-30% of the total solid content of the composition, the thermal initiator accounts for 1-10% of the total solid content of the composition, and the infrared absorber accounts for 1-10% of the total solid content of the composition; The thermal initiator is an iodonium salt or a sulfonium salt, and has a decomposition temperature of 150-220℃; the infrared absorber is a cyanine dye having an absorption peak at 750-850nm; the infrared absorber and the thermal initiator are prone to migration in the image layer; the hydrophilic heat-sensitive resin is a branched polyolefin resin containing a hydrophilic group and an epoxy group; the cross-linkable prepolymer is a multifunctional acrylic monomer or a multifunctional polyurethane acrylic monomer; and the macrocyclic compound is a product obtained by urethane reaction of a resorcinol calixarene and an isocyanate acrylate. The isocyanate acrylate has the following structure: R 1 is a hydrogen atom or a methyl group, R 2 is an ester group, r is an integer from 1 to 3.

2. The processless thermal plate precursor according to claim 1, characterized in that: The urethane reaction is a reaction between the phenolic hydroxyl groups of the resorcinol calixarene and the isocyanate groups of the isocyanate acrylate, and the resorcinol calixarene contains more moles of phenolic hydroxyl groups than the isocyanate acrylate contains moles of isocyanate groups.

3. The processless thermal plate precursor according to claim 2, wherein: The reaction medium of the urethane reaction is a solvent containing no active hydrogen, the reaction catalyst is an organic metal compound or an amine, and the reaction temperature is 50-100℃. The isocyanate acrylate is isocyanate methacrylate ethyl ester, isocyanate acrylate ethyl ester or 2-(2-isocyanate ethoxy) methyl acrylate ethyl ester.

4. The processless thermal plate precursor of claim 1, wherein: A protective layer is further arranged on the imaging layer.

5. The processless thermal plate precursor according to any one of claims 1-4, wherein: The hydrophilic heat-sensitive resin is a discrete particle having a particle size of 50-200nm. The support is an aluminum plate base subjected to electrolytic roughening and anodic oxidation treatment.

6. The processless thermal plate precursor of claim 5, wherein: The hydrophilic heat-sensitive resin is a polyolefin resin containing at least anionic side groups in the copolymer chain, and containing hydrophilic copolymer units of allyl ether with anionic side groups or urea side group-containing acrylamide, and epoxy acrylate copolymer units.

7. The processless thermal plate precursor of claim 6, wherein: The anionic side groups in the copolymer chain of the hydrophilic heat-sensitive resin are polyalkylene sulfonic acid, polyalkylene sulfonic acid salt, polyalkylene phosphonic acid or polyalkylene phosphonic acid salt.

8. A processless thermal plate characterized by: The processless thermal plate precursor is prepared according to any one of claims 1-7.

9. The use of a processless thermal plate according to claim 8, characterized in that: After the thermal plate is scanned and exposed by a thermal CTP plate making machine, it is developed by water washing, and then mounted on a printing machine for printing or directly mounted on a printing machine for development by a dampening solution of the printing machine and printing.

Images