CN113831329B - Crosslinking agent and preparation method and application thereof - Google Patents
Crosslinking agent and preparation method and application thereof Download PDFInfo
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- CN113831329B CN113831329B CN202111303770.XA CN202111303770A CN113831329B CN 113831329 B CN113831329 B CN 113831329B CN 202111303770 A CN202111303770 A CN 202111303770A CN 113831329 B CN113831329 B CN 113831329B
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- thermosensitive
- crosslinking agent
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- 238000002360 preparation method Methods 0.000 title claims abstract description 13
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- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 25
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- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920006322 acrylamide copolymer Polymers 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 231100000481 chemical toxicant Toxicity 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 1
- RSJLWBUYLGJOBD-UHFFFAOYSA-M diphenyliodanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[I+]C1=CC=CC=C1 RSJLWBUYLGJOBD-UHFFFAOYSA-M 0.000 description 1
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- JVICFMRAVNKDOE-UHFFFAOYSA-M ethyl violet Chemical compound [Cl-].C1=CC(N(CC)CC)=CC=C1C(C=1C=CC(=CC=1)N(CC)CC)=C1C=CC(=[N+](CC)CC)C=C1 JVICFMRAVNKDOE-UHFFFAOYSA-M 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229940075529 glyceryl stearate Drugs 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 229940107698 malachite green Drugs 0.000 description 1
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229940057867 methyl lactate Drugs 0.000 description 1
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- QSNBIXOLKHEACL-UHFFFAOYSA-N n,n-dimethylacetamide;propan-2-one Chemical compound CC(C)=O.CN(C)C(C)=O QSNBIXOLKHEACL-UHFFFAOYSA-N 0.000 description 1
- DAHPIMYBWVSMKQ-UHFFFAOYSA-N n-hydroxy-n-phenylnitrous amide Chemical class O=NN(O)C1=CC=CC=C1 DAHPIMYBWVSMKQ-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229940075554 sorbate Drugs 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- JEVGKYBUANQAKG-UHFFFAOYSA-N victoria blue R Chemical compound [Cl-].C12=CC=CC=C2C(=[NH+]CC)C=CC1=C(C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 JEVGKYBUANQAKG-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Printing Plates And Materials Therefor (AREA)
Abstract
The invention provides a cross-linking agent, a preparation method and application thereof, wherein the cross-linking agent contains a urethane bond structure, and a coating polymer after a cross-linking reaction has the wear resistance of polyurethane resin; the cross-linking agent has epoxy bond with four-ring structure, high activity and strong hydrolysis resistance; the cross-linking agent contains caprolactam groups, and the caprolactam groups endow the cross-linking agent with certain hydrophilicity, so that the non-thermal cross-linked coating is easier to be removed by water, and the environment-friendly development is realized; the crosslinking agent has the property of releasing active isocyanate groups by heating, and can be crosslinked with active hydrogen in the polymer, such as hydrogen in hydroxyl groups.
Description
Technical Field
The invention belongs to the technical field of lithography, and particularly relates to a cross-linking agent, a preparation method and application thereof.
Background
For a long time, the printing industry, especially the packaging printing industry, in China is widely developed under the conditions of high consumption and high pollution. However, with the weakness of the ecosystem for human survival, the environment deteriorates, the resources are highly scarce, and the environment is not burdened in terms of both the resource stock and the environmental load. The printing and post-printing processing technology has the problem of environmental pollution. For example, the developing solution used for plate making before printing contains toxic chemical components, and common printing ink, car washing water and the like used for printing contain heavy metal elements such as lead, chromium, mercury and the like, so that certain harm is caused to human health. Therefore, green printing is strongly demanded.
Green printing has appeared in the late 80 s of the 20 th century in western countries represented by japan, the united states, germany, etc., and has been developed over twenty years from the conceptual discussion stage to the practical application stage, and has been greatly developed and matured from the concept, the technical standards, the equipment process, the raw materials and the software applications, etc. In developed European and American countries, green printing is a representation of the technological development level of the printing, and is an effective means for replacing the traditional printing mode which generates environmental pollution and high energy consumption.
The green printing is a printing mode which adopts environment-friendly materials and processes, causes less pollution in the printing process, saves resources and energy, is easy to recycle and recycle after the printed matter is abandoned, can be naturally degraded and has little influence on the ecological environment. The green printing requirements are coordinated with the environment, including the use of environmentally friendly printing materials, clean printing production processes, the safety of the printed matter to the user, and the recycling and recycling of the printed matter. Namely, the whole life cycle of the printed matter from raw materials, production, use, recovery and the like meets the environmental protection requirement.
Currently, green printing is leading to the development of the printing industry with its strong impact. However, the pre-press plate making has entered the CTP era, so environmental-friendly no-treatment CTP plate materials have become a focus of attention in the industry. The CTP plate without treatment is a true plate without treatment in the broad sense, namely, after the plate is exposed and imaged on the direct plate making equipment, the plate can be printed on the machine without any subsequent treatment procedure, and the chemical development and washing treatment are not needed. In a narrow sense, it means that the plate material does not need chemical development treatment after exposure and imaging on a direct plate making machine, but there are individual non-chemical treatment procedures, such as removal of plate material ablation scraps, treatment work of coating protective glue and the like.
Development of green, environmentally friendly printing consumables, particularly green environmentally friendly printing plates, is a major issue in the development of green printing.
Thermosensitive CTP plates have been widely used, from the first generation of preheating type negative thermosensitive plates to the second generation of mature preheating-free positive thermosensitive plates used in large quantities, and the development goal of the third generation of thermosensitive plate material technology is treatment-free. The development of the current printing plate is towards green and environment-friendly, and all the world large-scale printing plate manufacturers sequentially push CTP plate without (low) chemical treatment.
Classification of treatment-free CTP plates: at present, the number of the treatment-free CTP plates in the market is large, and according to the characteristics of the plates, the plates can be divided into the following two main types:
(1) And CTP plate is completely free of treatment. Refers to CTP plate material which can be directly printed on a machine after imaging on plate making equipment. According to different imaging modes, the method can be mainly divided into an ablative type non-processing CTP plate and a thermal polarity non-processing CTP plate.
(2) Environment-friendly developing type no-treatment CTP plate material. After the CTP plate is exposed and imaged on a plate making machine, the CTP plate is subjected to development treatment before being printed on the machine, chemical developing liquid is not needed in the treatment process, and the CTP plate can be developed by adopting clear water for cleaning or performing photoresist protection on the printing plate; or after the CTP plate is exposed and imaged on a plate making machine, developing is carried out on the printing machine by utilizing the wetting effect of the fountain solution, and the medicinal film of the non-image-text part is removed.
The development of the green and environment-friendly CTP plate has a lot of technical routes, and can be divided into a thermal ablation technology, a phase change technology and a hot melting technology. The thermal ablation technology refers to the process of ablating the oleophilic coating by infrared laser energy to expose the hydrophilic surface of the aluminum plate to form a hydrophilic area; the phase change technology refers to that the polymer is subjected to hydrophilic-lipophilic conversion by laser energy so as to realize ink and water separation; the hot melt technique is a technique in which thermoplastic polymer particles dispersed in a crosslinked hydrophilic layer are melted by laser energy, and are changed from hydrophilic to hydrophobic and lipophilic. .
Developing a chemical-treatment-free CTP plate technology: EP0980754 describes decarboxylation to achieve hydrophilic-hydrophobic transition techniques, but with poor printability. WO94/23954 describes hot-melt laminating techniques, but which are prone to fouling; US4004924 describes a mixture of thermoplastic hydrophobic particles and a hydrophilic binder, which is also not print-resistant; EP 2006-5-24 06114475.4 describes a hot melt thermoplastic particle, easily contaminating the fountain solution; US 2005-8-3 11/196, 124 describes a one-dimensional linear structure hydrophilic adhesive with low print; US 2006-7-27 11/494,235 describes a printing plate precursor containing hydrophilic groups and esterified allyl groups, but the ester groups are not resistant to ink attack.
Currently, the environment-friendly thermosensitive plate is divided into a double-layer plate and a single-layer plate.
The double-layer environment-friendly thermosensitive plate is generally a double-bond free radical imaging mechanism, and in order to reduce the blocking effect of oxygen on free radical reaction, the plate is provided with an oxygen blocking protective layer, and has the advantages of high printing force of the plate, but the disadvantage of needing double-layer coating, high control requirement on the production process, low product yield, environmental pollution caused by the treatment of defective products generated in the production process, and indirectly increased environmental protection pressure.
The single-layer environment-friendly thermosensitive plate is generally a non-oxygen polymerization inhibition imaging mechanism, and the plate does not need to be provided with an oxygen inhibition protective layer.
At present, the ubiquitous problem of environment-friendly thermosensitive plate: 1. dot recovery accuracy; 2. problems with low chemical development or on-press development capability; 3. color reproduction uniformity problems; 4. and 5, the problem of printing force and the problem of plate making contrast.
The problem of dot reduction precision is mainly reflected in accurately reducing the image dots; the problem of low chemical development or on-press development capability is mainly reflected in whether the thermosensitive plate can be developed by water washing after scanning and exposing in a thermosensitive CTP plate-making machine or can be directly loaded on a printer to be developed and printed by a printer fountain solution; the problem of color reproduction uniformity is mainly reflected in the ink quantity of printing plates for adsorbing different color inks, and the difference of the ink quantity is directly expressed as the color difference of printing products; the plate making contrast problem is reflected in whether the image reticle can be automatically identified by a printer computer system after the thermosensitive plate is subjected to scanning exposure by a thermosensitive CTP plate making machine.
Disclosure of Invention
In order to solve the problems, the invention provides a cross-linking agent, a preparation method and application thereof, wherein the cross-linking agent contains a urethane bond structure, and a coating polymer after a cross-linking reaction has the wear resistance of polyurethane resin; the cross-linking agent has epoxy bond with four-ring structure, high activity and strong hydrolysis resistance; the cross-linking agent contains caprolactam groups, and the caprolactam groups endow the cross-linking agent with certain hydrophilicity, so that the non-thermal cross-linked coating is easier to be removed by water, and the environment-friendly development is realized; the crosslinking agent has the property of releasing active isocyanate groups by heating, and can be crosslinked with active hydrogen in the polymer, such as hydrogen in hydroxyl groups.
The object of the invention is achieved in the following way: a crosslinking agent having the structure:
。
the cross-linking agent is prepared from dicyclohexylmethane diisocyanate, dibutyltin dilaurate, ethyl-3-oxabutyl cyclomethanol and epsilon-caprolactam.
The preparation method of the cross-linking agent comprises the steps of heating dicyclohexylmethane diisocyanate, dibutyltin dilaurate and a solvent to 35-80 ℃, dropwise adding ethyl-3-oxabutyl cyclomethanol for reaction, and then adding epsilon-caprolactam for reaction until the peak at the position of the active isocyanate group 2275 is detected to disappear by infrared spectrum, so as to obtain a solution containing the cross-linking agent.
The solvent is at least one of dimethylformamide, dimethylacetamide, acetone, butanone, 1, 4-butyrolactone and ethyl acetate.
The preparation method of the cross-linking agent comprises the steps of heating dicyclohexylmethane diisocyanate, dibutyl tin dilaurate and dimethylacetamide to 45-65 ℃, dropwise adding ethyl-3-oxetane methyl alcohol, reacting for 0.5-2 hours, then adding epsilon-caprolactam, reacting for 10-30 minutes, and reacting for 12-48 hours in an ice water bath until the peak at the 2275 position of the active isocyanate group is detected by infrared spectrum to disappear, thus obtaining the dimethylformamide solution containing the cross-linking agent.
In the preparation method of the cross-linking agent, 262.3g of dicyclohexylmethane diisocyanate, 3g of dibutyltin dilaurate and 491.7g of dimethylacetamide are added into a four-neck flask with a temperature control heating, mechanical stirring, condensing reflux and drying tube of 1000 ml g, 116.2g of 3-ethyl-3-oxetanyl methanol is dropwise added to the flask until 50 ℃ is reached, the reaction is carried out for 30 minutes, then 1 hour, 113.2g of epsilon-caprolactam is added, the reaction is carried out for 20 minutes, and the reaction is carried out for 48 hours under an ice water bath until the peak at the position of an active isocyanate group 2275 is detected by infrared spectrum, so as to obtain the dimethylformamide solution of the compound P with the solid content of 50%.
The application of the cross-linking agent.
A heat-sensitive plate comprising the above-described crosslinking agent.
Firstly, compared with the existing crosslinking agent, the crosslinking agent provided by the application: 1. the cross-linking agent contains a urethane bond structure, and the coating polymer (such as an image layer in a thermosensitive plate) after the cross-linking reaction has the advantages of good wear resistance and good ink affinity of polyurethane resin; 2. the cross-linking agent has epoxy bond with four-ring structure, and has high activity and strong hydrolysis resistance; 3. the cross-linking agent contains caprolactam group, and the caprolactam group endows the cross-linking agent with certain hydrophilicity, so that a non-thermal cross-linked coating (such as a non-image layer in a thermosensitive plate) is easier to be removed by water, and green and environment-friendly development is realized; 4. the crosslinking agent has the property of releasing active isocyanate groups by heating, and can be crosslinked with active hydrogen in the polymer, such as hydrogen in hydroxyl groups. The heat-sensitive layer can be used for heat-sensitive plates, and can also be used as a radiation curing cross-linking agent in other fields, such as the fields of paint, adhesive and the like.
In addition, the heat-sensitive plate improves the imaging capability of the plate by adding the special cross-linking agent designed by the application, and the plate has a double imaging mechanism of cationic polymerization and urethanization reaction. The laser heat energy transfers energy to a thermal initiator through a thermal dye, and cations generated by heterolysis of the thermal initiator enable epoxy bonds in a crosslinking agent and epoxy bonds on cyclohexyl groups in special thermal resin to generate cation network crosslinking, so that cation network thermal imaging is realized; meanwhile, the plate has urethanization reticular thermal imaging capability, the cross-linking agent removes caprolactam groups at the tail end under the action of laser heat to release active isocyanate groups, and the active isocyanate groups can perform urethanization reaction with hydroxyl groups on special thermal resin, so that a thermosetting urethane bond reticular structural image is formed, and the sensitivity and the printing durability of the plate are improved.
Detailed Description
A crosslinking agent having the following structure (code; crosslinking agent P):
。
the cross-linking agent is prepared from dicyclohexylmethane diisocyanate, dibutyltin dilaurate, ethyl-3-oxabutyl cyclomethanol and epsilon-caprolactam. Since the synthesized crosslinking agent is a precise compound, it is sufficient that the specific compound can be synthesized depending on the raw materials, and the ratio of the raw materials only affects the yield of the product.
The preparation method of the cross-linking agent comprises the steps of heating dicyclohexylmethane diisocyanate, dibutyltin dilaurate and a solvent to 35-80 ℃, dropwise adding ethyl-3-oxabutyl cyclomethanol for reaction, and then adding epsilon-caprolactam for reaction until the peak at the position of the active isocyanate group 2275 is detected to disappear by infrared spectrum, so as to obtain a solution containing the cross-linking agent.
The preparation method of the cross-linking agent comprises the steps of heating dicyclohexylmethane diisocyanate, dibutyl tin dilaurate and dimethylacetamide to 45-65 ℃, dropwise adding ethyl-3-oxetane methyl alcohol, reacting for 0.5-2 hours, then adding epsilon-caprolactam, reacting for 10-30 minutes, and reacting for 12-48 hours in an ice water bath until the peak at the 2275 position of the active isocyanate group is detected by infrared spectrum to disappear, thus obtaining the dimethylformamide solution containing the cross-linking agent.
The solvent may be dimethylformamide, dimethylacetamide, acetone, butanone, 1, 4-butyrolactone, ethyl acetate, etc.
Besides the application of the heat-sensitive plate of the invention, the cross-linking agent can also be used as a radiation curing cross-linking agent in other fields, such as the fields of coating, adhesive and the like.
A heat-sensitive plate comprising the above-described crosslinking agent.
The heat-sensitive plate containing the cross-linking agent can be an environment-friendly heat-sensitive plate, and the plate comprises a hydrophilic carrier and a heat-sensitive layer, wherein the heat-sensitive layer contains heat-sensitive resin, the cross-linking agent, a thermal initiator and heat-sensitive color-changing dye.
The environment-friendly thermosensitive plate improves the imaging capability of the plate by adding the special cross-linking agent designed by the application, and the plate has a double imaging mechanism of cationic polymerization and urethanization reaction. The laser heat energy transfers energy to a thermal initiator through a thermal dye, and cations generated by heterolysis of the thermal initiator enable epoxy bonds in a crosslinking agent and epoxy bonds on cyclohexyl groups in special thermal resin to generate cation network crosslinking, so that cation network thermal imaging is realized; meanwhile, the plate has urethanization reticular thermal imaging capability, the cross-linking agent removes caprolactam groups at the tail end under the action of laser heat to release active isocyanate groups, and the active isocyanate groups can perform urethanization reaction with hydroxyl groups on special thermal resin, so that a thermosetting urethane bond reticular structural image is formed, and the sensitivity and the printing durability of the plate are improved. The cross-linking agent accounts for 5% -30%, preferably 10% -20% of the total solid content of the thermosensitive layer composition.
The design of a thermosensitive plate material firstly considers a thermosensitive coating of the plate material, wherein an important binder, namely functional film-forming resin, is needed in the thermosensitive coating, and the resin can ensure that the coating liquid of the thermosensitive coating is dried and then forms a film, so that the thermosensitive coating is attached to a hydrophilic carrier. The binder may be in a solution state or an emulsion state. Meanwhile, the functional film-forming resin contains functional groups and plays a special function role, and the thermosensitive resin is the adhesive.
The thermosensitive resin is monomer a: methacrylamide, monomer b: hydroxyethyl acrylamide and monomer c: the ternary radical copolymer of 3, 4-epoxycyclohexyl methacrylate, wherein the weight proportion of the methacrylamide unit in the copolymer is 40-80 percent (weight percent), the weight proportion of the hydroxyethyl acrylamide unit in the copolymer is 10-30 percent (weight percent), and the weight proportion of the 3, 4-epoxycyclohexyl methacrylate unit in the copolymer is 10-30 percent (weight percent). The thermosensitive resin accounts for 50-90%, preferably 60-80% of the total solid content of the thermosensitive layer.
The thermosensitive resin contains a hydrophilic structural unit, namely a methacrylamide unit, and the molecular weight of a thermosensitive layer is rapidly increased after infrared laser scanning imaging, so that a coating is firmer, and the coating after laser thermal exposure is difficult to remove by water and ink; the redundant coating of the unexposed blank part is easy to remove by water due to the existence of amide groups, and the blank part is exposed to be hydrophilic aluminum plate base, so that the environmental protection purpose of no pollutant discharge in the plate making process is realized. The weight percentage of the methacrylamide units in the copolymer is 40-80 percent (weight percentage).
The heat-sensitive resin contains a hydroxyethyl acrylamide structural unit, the hydroxyethyl acrylamide has good hydrophilicity and oil resistance, the water or fountain solution developing capability of the printing plate and the capability of resisting chemical etching in printing ink can be improved, and simultaneously, the hydroxyl in the hydroxyethyl acrylamide can be subjected to crosslinking reaction with isocyanate groups thermally released by a crosslinking agent, so that the image layer has a thermosetting urethane bond network structure, and the printing force of the heat-sensitive resin is higher than that of the traditional linear polymerization thermoplastic printing plate. The content of the hydroxyethyl acrylamide copolymer unit b in the copolymer is 10-30 percent by weight.
The special thermosensitive resin designed by the invention contains epoxy bonds on cyclohexyl, has high-efficiency cationic crosslinking capability, and transfers laser heat energy to a thermal initiator through the thermosensitive color-changing dye, so that the thermal initiator is heterolytic to generate cations, and the epoxy bonds on the cyclohexyl in the special thermosensitive resin and the epoxy bonds in the crosslinking agent are crosslinked and polymerized. The epoxy bond on the cyclohexyl contained in the thermosensitive resin has ultrahigh cationic crosslinking capability, and the cyclohexyl has certain rigidity, so that the wear resistance of a plate coating can be improved, and the printing endurance of the plate can be improved. The content of the copolymerized unit c containing the epoxy bond on the cyclohexyl group in the multipolymer is 10-30% by weight.
The heat-sensitive resin is synthesized by adopting a solution or emulsion copolymerization method, wherein the copolymerization reaction can be random copolymerization or block copolymerization, and random copolymerization is preferred. The initiator for polymerization includes peroxides such as di-t-butyl peroxide, benzoyl peroxide, persulfates such as potassium persulfate, amine persulfate, azo compounds such as azobisisobutyronitrile, etc., and the copolymerization is preferably solution polymerization.
The reaction solvent selected is water, methanol, ethanol, N-propanol, isopropanol, butanol, acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, butyl acetate, tetrahydrofuran, 1, 4-dioxane, N-dimethylformamide, dimethylacetamide acetone, methyl ethyl ketone, cyclohexane, ethylene dichloride, toluene, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol dimethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, acetylacetone, diacetone alcohol, ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol isopropyl ether, ethylene glycol butyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, dimethyl sulfoxide, methyl lactate, ethyl lactate, etc., or a mixture thereof. The copolymerization temperature is preferably 40 to 100℃and most preferably 60 to 90 ℃.
The weight average molecular weight of the thermosensitive resin is 4000-150000, and the glass transition temperature is 110-130 ℃.
The thermosensitive resin provided by the application is a functional film-forming resin which is an important binder in thermosensitive coatings for forming a thermosensitive layer, and the resin can form a film after the coating liquid for guaranteeing the thermosensitive coating is dried, so that the thermosensitive coating is attached to a hydrophilic carrier to form the thermosensitive layer. The binder may be in a solution state or an emulsion state. Meanwhile, the functional film-forming resin contains a hydrophilic unit of methacrylamide and hydroxyethylacrylamide, can realize water development or on-press development, and is a green and environment-friendly thermosensitive plate. In addition, the water or fountain solution developing capability and the chemical etching resistance in the printing ink of the printing plate can be improved, the image layer is provided with a thermosetting urethane bond net structure, the printing force is higher than that of the traditional linear polymerization thermoplastic printing plate, the wear resistance of the coating of the printing plate can be improved, and the printing force of the printing plate is improved.
The thermal initiator in the plate thermosensitive layer is described in detail below.
The plate has cationic polymerization imaging capability, so the thermal initiator herein is also referred to as a cationic photopolymerization initiator, and is selected from onium salts such as sulfonium salts, iodonium salts, and the like. Suitable onium salts include sulfonium salts, oxomaple onium salts, oxosulfonium salts, sulfoxides, diazonium salts, and halonium salts such as iodonium salts and the like. Specific examples of suitable onium salts are: diphenyliodonium chloride, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, 4- [ (2-hydroxytetradecyl-oxy ] -phenyl ] phenyliodonium hexafluoroantimonate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium iodonium octylsulfate, 2-methoxy-4-aminophenyl diazonium hexafluorophosphate, phenoxyphenyl diazonium hexafluoroantimonate, etc., the cationic photopolymerization initiator of the present invention is one or more selected from iodonium salts and sulfonium hexafluoroantimonate, and has a thermal decomposition temperature of 150 to 200. The cationic photopolymerization initiator preferably accounts for 1 to 15% of the dry weight of the coating film (i.e., the total solid amount of the composition of the thermosensitive layer) in the thermosensitive layer, preferably 1 to 10%.
The components of the thermosensitive layer of the thermosensitive plate of the present invention are described in detail below: thermochromic dyes.
The component thermochromic dye in the thermosensitive plate composition has the functions of infrared dye and laser color change, and mainly plays roles of energy transfer and color change. The heat of the infrared laser transmits laser energy to a thermal initiator through the thermochromic dye, and the thermal initiator generates epoxy group polymerization in a cation initiation system to realize thermal imaging. The laser energy is converted into heat energy through the thermosensitive dye, the caprolactam group at the tail end of the crosslinking agent is removed, the active isocyanate group is released, and the active isocyanate group can be subjected to urethanization reaction with the hydroxyl group on the special thermosensitive resin, so that a thermosetting urethane bond network structure image is formed. Meanwhile, the thermosensitive color-changing dye has the function of laser color change, and can perform ring-closing reaction under the action of laser heat, so that color change occurs, the color conversion is irreversible, the non-development type contrast presentation of the printing plate is realized, the defect of image of the printing plate can be detected by naked eyes of a printing operator, and meanwhile, the automatic positioning and identification of a modern highly intelligent printing machine can be realized, and the automatic intelligent printing is realized. The thermochromic dye of the present invention may be a thermochromic azamethine dye. Thermochromic azamethine dyes having absorption peaks in the range of 730 to 880nm, preferably azamethine dyes of the following structure (code: thermochromic dye D):
The thermochromic dye preferably occupies 1 to 15 percent, preferably 5 to 10 percent of the dry weight of the coating film in the thermosensitive layer.
Finally, the hydrophilic support of the thermosensitive plate according to the invention is described in detail.
The thermosensitive layer composition of the present invention is coated on a thermosensitive plate hydrophilic support, which includes a metal plate base such as a copper plate base, an aluminum plate base, and the like. The hydrophilic carrier selected by the invention is an aluminum plate base subjected to electrolytic roughening, anodic oxidation and hole sealing treatment, and the average roughness of the center line is 0.3-0.6um, and the hydrophilic carrier is prepared through electrolytic roughening. The aluminum plate base is 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.l% of titanium. The electrolytic coarsening electrolyte may be an aqueous solution of an acid, base or salt. Firstly, placing the aluminum plate in 1% -30% aqueous solution of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate and the like, and chemically corroding at 20-80 ℃ for 5-250 seconds. Then neutralizing in 10% -30% nitric acid or sulfuric acid at 20-70deg.C to remove ash. At 10-60deg.C, electrolysis is carried out in electrolyte of nitric acid or hydrochloric acid at current density of 5-100A/dm 2 for 10-300 s by rectangular wave, mesa wave or sine wave with alternately changed positive and negative polarities. Then, an anodic oxidation treatment is performed. Anodic oxidation is usually carried out by a sulfuric acid method, the concentration of sulfuric acid is 5-30%, the current density is 1-15A/dm 2, the oxidation temperature is 20-60 ℃, the oxidation time is 5-250 seconds, so as to form an oxide film of 1-10g/m 2, and finally hole sealing treatment is carried out. The pore-sealing treatment may be carried out by various methods, preferably by sealing 50-80% by volume of the micropores of the oxide film, and finally by coating polyvinyl phosphonic acid on the aluminum plate subjected to the above treatment, with a thickness of 3mg/m 2.
The thermosensitive layer composition of the present invention may be produced by adding other necessary auxiliary agents such as solvents, inhibitors of ordinary temperature thermal polymerization, surfactants, etc. The solvent is mainly used for preparing thermosensitive coating photosensitive liquid and comprises the following components: alcohols, ketones, esters, ethers, amides, aromatic solvents, ethylene dichloride, tetrahydrofuran, and the like, the solvents being used in pure or mixed form; the normal temperature thermal polymerization inhibitor is used for preventing the plate from polymerizing at normal temperature and improving the normal temperature stability of the plate. The thermal polymerization inhibitor includes: hydroquinone, nitroxide piperidinol, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4 '-thiobis- (3-methyl-6-t-butylphenol), 2' -methylenebis (4-methyl-16-t-butylphenol), and primary cerium salts of N-nitrosophenyl hydroxylamine, and the like; the layer coloring agent is added to increase the image density of the thermosensitive plate after plate making, so as to facilitate the visual inspection or image analysis measurement of the thermosensitive plate after plate making, and the device comprises: methyl violet, ethyl violet, crystal violet, intracrystalline violet, victoria blue, oil green, oil blue, oil yellow, rhodamine B, methyl violet, malachite green, methylene blue, triazines, and the like; the coating also needs to be added with a surfactant, and nonionic surfactants, amphoteric surfactants, silicon-containing surfactants, fluorine-containing surfactants and the like, such as betaines, glyceryl stearate, brown oil sorbate, polysiloxanes and polyfluoroalkyl ethers.
The thermosensitive layer composition of the present invention is generally applied by techniques known in the art (e.g., knife coating, bar coating, roll coating, press coating, etc.).
The application adopts the thermosensitive resin, the cross-linking agent and the thermosensitive color-changing dye with special structures, improves the sensitivity of the thermosensitive plate through a double imaging mechanism of cationic polymerization and urethanization reaction, and improves the dot reduction precision of the plate; the cross-linking agent is introduced into a thermosetting high-wear-resistance urethane bond net-shaped cross-linking structure, so that the cross-linking density of the image layer is improved, the printing durability of the printing plate is improved, and the problem of color reduction uniformity of the image layer is solved by improving the exposure latitude; improving the developability and the printability of the plate material by introducing an amide group; the plate making contrast of the plate is improved by adopting the thermochromic dye with a special structure, so that the problem of automatic plate identification by a computer is solved; meanwhile, the plate has hydrophilicity, can realize water development or fountain solution development, and is a green and environment-friendly thermosensitive plate.
The present invention will now be described in detail with reference to specific examples, which are given herein for further illustration only and are not to be construed as limiting the scope of the invention, since numerous insubstantial modifications and adaptations thereof will now occur to those skilled in the art in light of the foregoing disclosure.
The following are synthetic examples of the present invention, but the present invention is not limited to the following examples.
The raw materials are available from the following companies: methacrylamide, hydroxyethyl acrylamide: technology of Shanghai carbofuran; 3, 4-epoxycyclohexyl methacrylate CMA: mitsubishi yang chemistry of japan; dimethylacetamide DMAC: lanzhou petrochemical, azobisisobutyronitrile AIBN: tianjin Fuchen chemical reagent; benzoyl peroxide BPO: laiwukang new agent.
A first part: synthesis examples L1 to L11 of Special thermosensitive resin (code L)
Example 1 (Special thermosensitive resin L1)
300G of dimethylacetamide, 80g (80 wt%) of methacrylamide, 10g (10 wt%) of hydroxyethylacrylamide, 10g (10 wt%) of 3, 4-epoxycyclohexyl methacrylate and 1g of azobisisobutyronitrile are added into a 500 ml four-neck flask with a temperature control heating device, a mechanical stirring device, a condensation reflux device and a nitrogen protection device, the materials are uniformly stirred, the reaction is carried out for 8 hours at 70 ℃, the reaction is completed after the temperature reduction, and the reaction stock solution can be directly used.
Example 2 (Special thermosensitive resin L2)
300G of dimethylacetamide, 70g (70 wt%) of methacrylamide, 20g (20 wt%) of hydroxyethylacrylamide, 10g (10 wt%) of 3, 4-epoxycyclohexyl methacrylate and 1g of azobisisobutyronitrile are added into a 500 ml four-neck flask with a temperature control heating device, a mechanical stirring device, a condensation reflux device and a nitrogen protection device, the materials are uniformly stirred, the reaction is carried out for 8 hours at 70 ℃, the reaction is completed after the temperature reduction, and the reaction stock solution can be directly used.
Example 3 (Special thermosensitive resin L3)
300G of dimethylacetamide, 70g (70 wt%) of methacrylamide, 10g (10 wt%) of hydroxyethylacrylamide, 20g (20 wt%) of 3, 4-epoxycyclohexyl methacrylate and 1g of azobisisobutyronitrile are added into a 500 ml four-neck flask with a temperature control heating device, a mechanical stirring device, a condensation reflux device and a nitrogen protection device, the materials are uniformly stirred, the reaction is carried out for 8 hours at 70 ℃, the reaction is completed after the temperature reduction, and the reaction stock solution can be directly used.
Example 4 (Special thermosensitive resin L4)
300G of dimethylacetamide, 70g (70 wt%) of methacrylamide, 15g (15 wt%) of hydroxyethyl acrylamide, 15g (15 wt%) of 3, 4-epoxycyclohexyl methacrylate and 1g of azobisisobutyronitrile are added into a 500 ml four-neck flask with a temperature control heating device, a mechanical stirring device, a condensation reflux device and a nitrogen protection device, the materials are uniformly stirred, the reaction is carried out for 8 hours at 70 ℃, the reaction is completed after the temperature reduction, and the reaction stock solution can be directly used.
Example 5 (Special thermosensitive resin L5)
300G of dimethylacetamide, 60g (60 wt%) of methacrylamide, 30g (30 wt%) of hydroxyethylacrylamide, 10g (10 wt%) of 3, 4-epoxycyclohexyl methacrylate and 1g of azobisisobutyronitrile are added into a 500 ml four-neck flask with a temperature control heating device, a mechanical stirring device, a condensation reflux device and a nitrogen protection device, the materials are uniformly stirred, the reaction is carried out for 8 hours at 70 ℃, the reaction is completed after the temperature reduction, and the reaction stock solution can be directly used.
Example 6 (Special thermosensitive resin L6)
300G of dimethylacetamide, 60g (60 wt%) of methacrylamide, 10g (10 wt%) of hydroxyethylacrylamide, 30g (30 wt%) of 3, 4-epoxycyclohexyl methacrylate and 1g of azobisisobutyronitrile are added into a 500 ml four-neck flask with a temperature control heating device, a mechanical stirring device, a condensation reflux device and a nitrogen protection device, the materials are uniformly stirred, the reaction is carried out for 8 hours at 70 ℃, the reaction is completed after the temperature reduction, and the reaction stock solution can be directly used.
Example 7 (Special thermosensitive resin L7)
300G of dimethylacetamide, 60g (60 wt%) of methacrylamide, 20g (20 wt%) of hydroxyethyl acrylamide, 20g (20 wt%) of 3, 4-epoxycyclohexyl methacrylate and 1g of azobisisobutyronitrile are added into a 500 ml four-neck flask with a temperature control heating device, a mechanical stirring device, a condensation reflux device and a nitrogen protection device, the materials are uniformly stirred, the reaction is carried out for 8 hours at 70 ℃, the reaction is completed after the temperature reduction, and the reaction stock solution can be directly used.
Example 8 (Special thermosensitive resin L8)
300G of dimethylacetamide, 50g (50 wt%) of methacrylamide, 20g (20 wt%) of hydroxyethylacrylamide, 30g (30 wt%) of 3, 4-epoxycyclohexyl methacrylate and 1g of azobisisobutyronitrile are added into a 500 ml four-neck flask with a temperature control heating device, a mechanical stirring device, a condensation reflux device and a nitrogen protection device, the materials are uniformly stirred, the reaction is carried out for 8 hours at 70 ℃, the reaction is completed after the temperature reduction, and the reaction stock solution can be directly used.
Example 9 (Special thermosensitive resin L9)
300G of dimethylacetamide, 50g (50 wt%) of methacrylamide, 30g (30 wt%) of hydroxyethylacrylamide, 20g (20 wt%) of 3, 4-epoxycyclohexyl methacrylate and 1g of azobisisobutyronitrile are added into a 500 ml four-neck flask with a temperature control heating device, a mechanical stirring device, a condensation reflux device and a nitrogen protection device, the materials are uniformly stirred, the reaction is carried out for 8 hours at 70 ℃, the reaction is completed after the temperature reduction, and the reaction stock solution can be directly used.
Example 10 (Special thermosensitive resin L10)
300G of dimethylacetamide, 50g (50 wt%) of methacrylamide, 25g (25 wt%) of hydroxyethyl acrylamide, 25g (25 wt%) of 3, 4-epoxycyclohexyl methacrylate and 1g of azobisisobutyronitrile are added into a 500 ml four-neck flask with a temperature control heating device, a mechanical stirring device, a condensation reflux device and a nitrogen protection device, the materials are uniformly stirred, the reaction is carried out for 8 hours at 70 ℃, the reaction is completed after the temperature reduction, and the reaction stock solution can be directly used.
Example 11 (Special thermosensitive resin L11)
300G of dimethylacetamide, 40g (40 wt%) of methacrylamide, 30g (30 wt%) of hydroxyethyl acrylamide, 30g (30 wt%) of 3, 4-epoxycyclohexyl methacrylate and 1g of azobisisobutyronitrile are added into a 500 ml four-neck flask with a temperature control heating device, a mechanical stirring device, a condensation reflux device and a nitrogen protection device, the materials are uniformly stirred, the reaction is carried out for 8 hours at 70 ℃, the reaction is completed after the temperature reduction, and the reaction stock solution can be directly used.
Comparative examples 1-5 (synthetic like the Ikefir polymers A1-A5):
according to the description of the patent EP 2006-5-24 06114475.4, polymers similar to those of Ikefir are synthesized by solution polymerization, but without hydrophilic groups, the polymer structure:
A1: 400 methyl ethyl ketone, 5g of sodium dodecyl sulfate, 80g (80 wt%) of ST (styrene), 20g (20 wt%) of AN (acrylonitrile) and 0.7g of AIBN (azobisisobutyronitrile) are added into a four-necked flask with a temperature-controlled heating, mechanical stirring, condensation reflux and nitrogen protection device of 1000 ml, the mixture is added dropwise at 80 ℃ for 0.5 hour, 0.3g of AIBN (azobisisobutyronitrile) is added after the mixture is reacted for 7.5 hours again, and the reaction is continued for 12 hours again, and then the reaction is finished.
Changing the feeding proportion and synthesizing the like Aikefa polymer:
A2(ST:60,AN:40), A3(ST:50,AN:50) , A4(ST:40,AN:60),A5(ST:20,AN:80) 。
comparative examples 6-10 (synthetic analogous kodak polymers K1-K5):
according to kodak patent US 2005-8-3 11/196, a polymer similar to an alike polymer is produced by solution polymerization, the polymer contains hydrophilic groups but no epoxy groups, and the polymer structure:
K1: 400g of methyl ethyl ketone, 80g (80 wt%) of ST (styrene), 10g (10 wt%) of AN (acrylonitrile), 10g (0.7 g) (10 wt%) of PEGMA45 (polyethoxy methacrylate, polymerization degree N=45) and AIBN (azobisisobutyronitrile) were added dropwise to a 1000 ml four-necked flask equipped with a temperature-controlled heating, mechanical stirring, condensation reflux and nitrogen protection device, the mixture was allowed to react for a further 7.5 hours, and 0.3g of AIBN (azobisisobutyronitrile) was added dropwise thereto at 80℃to continue the reaction for a further 12 hours.
Changing the feeding ratio and the reaction concentration to synthesize the similar Kodak polymer:
K2(ST/AN/PEFMA=70/15/15,N=55),K3(ST/AN/PEFMA=60/20/20,N=45), K4(ST/AN/PEFMA=50/40/100,N=55), K5(ST/AN/PEFMA=30/60/10,N=65)
Thermochromic dyes D of the above structure are commercially available from Shenyang chemical institute.
The infrared absorbing dye ADS830 used in the comparative example is commercially available from Qingdao blue Sail New Material company and has the following structure:
a second part: synthesis of crosslinker P
The raw materials are available from the following companies: dicyclohexylmethane diisocyanate: german bayer chemistry; 3-ethyl-3-oxabutyl cyclomethanol: nantong New Naxi New Material Co., ltd; epsilon-caprolactam: technology of Shanghai carbofuran; dibutyl tin dilaurate: tianjin chemical reagent II plant; dimethylacetamide: lanzhou petrochemical industry.
Example 1:
A four-necked flask with a temperature-controlled heating, mechanical stirring, condensing reflux and drying tube of 1000 ml is filled with 262.3g of dicyclohexylmethane diisocyanate, 3g of dibutyltin dilaurate and 491.7g of dimethylacetamide, 116.2g of 3-ethyl-3-oxetanone methanol are dropwise added at 50 ℃ for 30 minutes, the reaction is carried out for 1 hour, then 113.2g of epsilon-caprolactam is added, the reaction is carried out for 20 minutes, and the reaction is carried out for 48 hours under an ice water bath until the peak at the active isocyanate group 2275 is detected by infrared spectrum, so that a dimethylformamide solution of the compound P with the solid content of 50% is obtained, and the solution can be directly used according to the solid content. The product synthesized in example 1 is the crosslinker used in the third example, where 50% solids is weight content and the other 50% is convenient for later testing.
The synthesis of the crosslinker P may also be as follows in examples 2 to 6.
Example 2:
Dicyclohexylmethane diisocyanate, dibutyltin dilaurate and a solvent are heated to 35-80 ℃, ethyl-3-oxetane methyl alcohol is dropwise added for reaction, epsilon-caprolactam is then added for reaction until the peak at the 2275 position of the active isocyanate group is detected to disappear through infrared spectrum, and a solution containing a cross-linking agent is obtained.
Example 2:
A four-necked flask with a temperature-controlled heating, mechanical stirring, condensing reflux and drying tube of 1000 ml was charged with 262.3g of dicyclohexylmethane diisocyanate, 3g of dibutyltin dilaurate and 491.7g of dimethylacetamide, 116.2g of 3-ethyl-3-oxetanyl methanol was added dropwise thereto by heating to 35℃for 35 minutes, the reaction was further carried out for 0.5 hour, then 113.2g of ε -caprolactam was added thereto, the reaction was carried out for 10 minutes, and the reaction was carried out under an ice-water bath for 12 hours until the disappearance of the peak at the active isocyanate group 2275 was detected by infrared spectrum, to obtain a dimethylformamide solution of compound P having a solid content of 50%.
Example 3:
A four-necked flask with a temperature-controlled heating, mechanical stirring, condensing reflux and drying tube of 1000 ml was charged with 262.3g of dicyclohexylmethane diisocyanate, 3g of dibutyltin dilaurate and 491.7g of dimethylacetamide, 116.2g of 3-ethyl-3-oxetanyl methanol was added dropwise thereto by heating to 80℃for 32 minutes, the reaction was further carried out for 1.5 hours, then 113.2g of ε -caprolactam was added thereto, the reaction was carried out for 15 minutes, and the reaction was carried out under an ice-water bath for 18 hours until the disappearance of the peak at the active isocyanate group 2275 was detected by infrared spectrum, to obtain a dimethylformamide solution of compound P having a solid content of 50%.
Example 4:
A four-necked flask with a temperature-controlled heating, mechanical stirring, condensing reflux and drying tube of 1000 ml was charged with 262.3g of dicyclohexylmethane diisocyanate, 3g of dibutyltin dilaurate and 491.7g of dimethylacetamide, 116.2g of 3-ethyl-3-oxetanyl methanol was added dropwise thereto by heating to 65℃for 30 minutes, the reaction was further carried out for 2 hours, then 113.2g of ε -caprolactam was added thereto, the reaction was carried out for 25 minutes, and the reaction was carried out under an ice-water bath for 36 hours until the disappearance of the peak at the active isocyanate group 2275 was detected by infrared spectrum, to obtain a dimethylformamide solution of compound P having a solid content of 50%.
Example 5:
A four-necked flask with a temperature-controlled heating, mechanical stirring, condensing reflux and drying tube of 1000 ml was charged with 262.3g of dicyclohexylmethane diisocyanate, 3g of dibutyltin dilaurate and 491.7g of butanone, 116.2g of 3-ethyl-3-oxetanyl methanol was added dropwise thereto for 32 minutes, the reaction was further carried out for 1.8 hours, then 113.2g of ε -caprolactam was added thereto, the reaction was carried out for 30 minutes, and the reaction was carried out under an ice-water bath for 36 hours until the disappearance of the peak at the active isocyanate group 2275 was detected by infrared spectrum, to obtain a dimethylformamide solution of compound P having a solid content of 50%.
Example 6:
A four-necked flask with a temperature-controlled heating, mechanical stirring, condensing reflux and drying tube of 1000 ml was charged with 262.3g of dicyclohexylmethane diisocyanate, 3g of dibutyltin dilaurate, 491.7g of 1, 4-butyrolactone, and 116.2g of 3-ethyl-3-oxetanyl-methanol was added dropwise thereto by heating to 70℃for 32 minutes, followed by further reaction for 2 hours, then 113.2g of ε -caprolactam was added thereto, and the reaction was carried out for 25 minutes under an ice water bath for 48 hours until the disappearance of the peak at the reactive isocyanate group 2275 was detected by infrared spectrum, to give a dimethylformamide solution of compound P having a solid content of 50%.
Example 7
A four-necked flask with a temperature-controlled heating, mechanical stirring, condensing reflux and drying tube of 1000 ml was charged with 262.3g of dicyclohexylmethane diisocyanate, 3g of dibutyltin dilaurate and 491.7g of ethyl acetate, 116.2g of 3-ethyl-3-oxetanyl methanol was added dropwise thereto for 32 minutes, the reaction was further carried out for 1.8 hours, then 113.2g of ε -caprolactam was added thereto, the reaction was carried out for 15 minutes and the reaction was carried out under an ice-water bath for 48 hours until the disappearance of the peak at the active isocyanate group 2275 was detected by infrared spectrum, to obtain a dimethylformamide solution of compound P having a solid content of 50%.
Example 8
A four-necked flask with a temperature-controlled heating, mechanical stirring, condensing reflux and drying tube of 1000 ml was charged with 262.3g of dicyclohexylmethane diisocyanate, 3g of dibutyltin dilaurate and 491.7g of acetone, 116.2g of 3-ethyl-3-oxetanyl methanol was added dropwise thereto for 32 minutes, the reaction was further carried out for 1.6 hours, then 113.2g of ε -caprolactam was added thereto, the reaction was carried out for 20 minutes and the reaction was carried out under an ice-water bath for 48 hours until the disappearance of the peak at the active isocyanate group 2275 was detected by infrared spectrum, to obtain a dimethylformamide solution of compound P having a solid content of 50%.
The amounts of the raw materials used in examples 2 to 8 may be varied, but only the yield of the crosslinking agent P may be affected.
Third section: preparation of thermosensitive plate
Example 1
Preparation of a plate base: a1050 rolled aluminum plate having a purity of 99.5% and a thickness of 0.3mm was etched in a 5% aqueous sodium hydroxide solution at 70℃for 20 seconds, rinsed with running water, and immediately neutralized with A1% aqueous nitric acid solution. Then, the mixture was electrolytically roughened with a sine wave alternating current at 40℃in a 1% aqueous hydrochloric acid solution at a current density of 50A/dm 2 for 16 seconds, followed by neutralization with a 5% aqueous sodium hydroxide solution at 40℃for 10 seconds, and washed with water. Finally, the mixture was anodized with a 20% aqueous sulfuric acid solution at 30℃for 20 seconds at a current density of 15A/dm 2 and washed with water. The resulting plate was subjected to hole sealing treatment with a 5% sodium silicate aqueous solution at 80℃for 18 seconds, washed with water and dried to give a plate having a center line average roughness of 0.5. Mu.m, and an oxide film weight of 3.0g/dm 2.
Coating a thermosensitive layer: the following photosensitive liquid (i.e., thermosensitive layer composition) was extrusion coated on the above hydrophilized plate base, followed by drying at 100℃for 60 seconds, to obtain a coating dry weight of 10mg/dm 2. The following components (weight parts of each component) are used for the photosensitive liquid:
special heat-sensitive resin L1 90
Crosslinking agent P5
Diaryl hexafluorophosphate iodonium salt 3
Thermochromic dye D2
Basic brilliant blue 0.5
Surfactant (BYK 306) 0.5
Methyl ethyl ketone 200
1-Methoxy-2-propanol 700
Example 2
The substrate, thermosensitive layer were prepared in the same manner as above, and the following components were used for the photosensitive liquid:
Special thermosensitive resin L1 85
Crosslinking agent P10
Diaryl hexafluorophosphate iodonium salt 3
Thermochromic dye D2
Basic brilliant blue 0.5
Surfactant (BYK 306) 0.5
Methyl ethyl ketone 200
1-Methoxy-2-propanol 700
Example 3
The substrate, thermosensitive layer were prepared in the same manner as above, and the following components were used for the photosensitive liquid:
Special thermosensitive resin L1 80
Crosslinking agent P15
Diaryl hexafluorophosphate iodonium salt 3
Thermochromic dye D2
Basic brilliant blue 0.5
Surfactant (BYK 306) 0.5
Methyl ethyl ketone 200
1-Methoxy-2-propanol 700
Example 4
The substrate, thermosensitive layer were prepared in the same manner as above, and the following components were used for the photosensitive liquid:
Special thermosensitive resin L2 75
Crosslinking agent P20
Diaryl hexafluorophosphate iodonium salt 3
Thermochromic dye D2
Basic brilliant blue 0.5
Surfactant (BYK 306) 0.5
Methyl ethyl ketone 200
1-Methoxy-2-propanol 700
Example 5
The substrate, thermosensitive layer were prepared in the same manner as above, and the following components were used for the photosensitive liquid:
Special thermosensitive resin L2 70
Crosslinking agent P25
Diaryl hexafluorophosphate iodonium salt 3
Thermochromic dye D2
Basic brilliant blue 0.5
Surfactant (BYK 306) 0.5
Methyl ethyl ketone 200
1-Methoxy-2-propanol 700
Example 6
The substrate, thermosensitive layer were prepared in the same manner as above, and the following components were used for the photosensitive liquid:
Special thermosensitive resin L2 65
Crosslinking agent P30
Diaryl hexafluorophosphate iodonium salt 3
Thermochromic dye D2
Basic brilliant blue 0.5
Surfactant (BYK 306) 0.5
Methyl ethyl ketone 200
1-Methoxy-2-propanol 700
Example 7
The substrate, thermosensitive layer were prepared in the same manner as above, and the following components were used for the photosensitive liquid:
Special thermosensitive resin L3 60
Crosslinking agent P30
Diaryl hexafluorophosphate iodonium salt 5
Thermochromic dye D5
Basic brilliant blue 0.5
Surfactant (BYK 306) 0.5
Methyl ethyl ketone 200
1-Methoxy-2-propanol 700
Example 8
The substrate, thermosensitive layer were prepared in the same manner as above, and the following components were used for the photosensitive liquid:
Special thermosensitive resin L3 55
Crosslinking agent P15
Diaryl hexafluorophosphate iodonium salt 15
Thermochromic dye D15
Basic brilliant blue 0.5
Surfactant (BYK 306) 0.5
Methyl ethyl ketone 200
1-Methoxy-2-propanol 700
Example 9
The substrate, thermosensitive layer were prepared in the same manner as above, and the following components were used for the photosensitive liquid:
Special thermosensitive resin L3 50
Crosslinking agent P30
Diaryl hexafluorophosphate iodonium salt 10
Thermochromic dye D10
Basic brilliant blue 0.5
Surfactant (BYK 306) 0.5
Methyl ethyl ketone 200
1-Methoxy-2-propanol 700
Example 10
The substrate, thermosensitive layer were prepared in the same manner as above, and the following components were used for the photosensitive liquid:
Special thermosensitive resin L4 85
Crosslinking agent P10
Diaryl hexafluorophosphate iodonium salt 3
Thermochromic dye D2
Basic brilliant blue 0.5
Surfactant (BYK 306) 0.5
Methyl ethyl ketone 200
1-Methoxy-2-propanol 700
Example 11
The substrate, thermosensitive layer were prepared in the same manner as above, and the following components were used for the photosensitive liquid:
special thermosensitive resin L5 85
Crosslinking agent P10
Diaryl hexafluorophosphate iodonium salt 3
Thermochromic dye D2
Basic brilliant blue 0.5
Surfactant (BYK 306) 0.5
Methyl ethyl ketone 200
1-Methoxy-2-propanol 700
Example 12
The substrate, thermosensitive layer were prepared in the same manner as above, and the following components were used for the photosensitive liquid:
Special thermosensitive resin L6 85
Crosslinking agent P10
Diaryl hexafluorophosphate iodonium salt 3
Thermochromic dye D2
Basic brilliant blue 0.5
Surfactant (BYK 306) 0.5
Methyl ethyl ketone 200
1-Methoxy-2-propanol 700
Example 13
The substrate, thermosensitive layer were prepared in the same manner as above, and the following components were used for the photosensitive liquid:
special thermosensitive resin L7 85
Crosslinking agent P10
Diaryl hexafluorophosphate iodonium salt 3
Thermochromic dye D2
Basic brilliant blue 0.5
Surfactant (BYK 306) 0.5
Methyl ethyl ketone 200
1-Methoxy-2-propanol 700
Example 14
The substrate, thermosensitive layer were prepared in the same manner as above, and the following components were used for the photosensitive liquid:
Special thermosensitive resin L8 85
Crosslinking agent P10
Diaryl hexafluorophosphate iodonium salt 3
Thermochromic dye D2
Basic brilliant blue 0.5
Surfactant (BYK 306) 0.5
Methyl ethyl ketone 200
1-Methoxy-2-propanol 700
Example 15
The substrate, thermosensitive layer were prepared in the same manner as above, and the following components were used for the photosensitive liquid:
special thermosensitive resin L9 85
Crosslinking agent P10
Diaryl hexafluorophosphate iodonium salt 3
Thermochromic dye D2
Basic brilliant blue 0.5
Surfactant (BYK 306) 0.5
Methyl ethyl ketone 200
1-Methoxy-2-propanol 700
Example 16
The substrate, thermosensitive layer were prepared in the same manner as above, and the following components were used for the photosensitive liquid:
Special thermosensitive resin L10 85
Crosslinking agent P10
Diaryl hexafluorophosphate iodonium salt 4
Thermochromic dye D1
Basic brilliant blue 0.5
Surfactant (BYK 306) 0.5
Methyl ethyl ketone 200
1-Methoxy-2-propanol 700
Example 17
The substrate, thermosensitive layer were prepared in the same manner as above, and the following components were used for the photosensitive liquid:
special heat-sensitive resin L11 85
Crosslinking agent P10
Diaryl hexafluorophosphate iodonium salt 1
Thermochromic dye D4
Basic brilliant blue 0.5
Surfactant (BYK 306) 0.5
Methyl ethyl ketone 200
1-Methoxy-2-propanol 700
Example 18
A plate and a thermosensitive layer were prepared in the same manner as in example 1, except that the center line average roughness of the plate was made 0.4. Mu.m.
Example 19
A plate and a thermosensitive layer were prepared in the same manner as in example 1, except that the center line average roughness of the plate was made 0.6. Mu.m.
Example 20
A plate base, a thermosensitive layer was prepared in the same manner as in example 1, except that the dry coating weight of the photosensitive layer was 8mg/dm 2.
Example 21
A plate base, a thermosensitive layer were prepared in the same manner as in example 1, except that the dry coating weight of the photosensitive layer was 15mg/dm 2.
Comparative examples 1 to 5
A plate base, a thermosensitive layer were prepared in the same manner as in example 1. The following components were used for the photosensitive liquid:
Polymers A1 to A5 70
Pentaerythritol triacrylate 15
Hydroxypropyl cellulose 10
Diaryl hexafluorophosphate iodonium salt 2.5
Heat sensitive dye ADS830 1
Nitroxide radical piperidinol 0.5
Basic brilliant blue 0.5
Surfactant (BYK 306) 0.5
Methyl ethyl ketone 200
1-Methoxy-2-propanol 700
Namely, 70 parts of the polymers A1 to A5 are respectively used in sequence, and the other raw materials and the dosage are the same, so that the photosensitive liquids of the comparative examples 1 to 5 are respectively obtained in sequence.
Coating an oxygen barrier layer: the following oxygen barrier layer solution was extrusion coated on the thermosensitive layer obtained above, and then dried at 110℃for 60 seconds. 10mg/dm 2 of dry coating weight (parts by weight of the components) was obtained.
Oxygen barrier layer formula (weight portions of each component)
Polyvinyl alcohol PVA-205 (Japanese colali) 17
Polyvinylpyrrolidone PVPK30 (BASF Germany) 3
Emulsifier OP-10 (Hanm Germany) 0.45
Deionized water 480
Comparative examples 6 to 10
A plate base, a thermosensitive layer were prepared in the same manner as in example 1. The following components were used for the photosensitive liquid:
Polymers K1 to K5 70
Pentaerythritol triacrylate 25
Diaryl hexafluorophosphate iodonium salt 2.5
Heat sensitive dye ADS830 1
Nitroxide radical piperidinol 0.5
Basic brilliant blue 0.5
Surfactant (BYK 306) 0.5
Methyl ethyl ketone 200
1-Methoxy-2-propanol 700
Namely, 70 parts of the polymers K1-K5 are respectively used in sequence, and the other raw materials and the dosage are the same, so that the photosensitive solutions of comparative examples 6-10 are respectively obtained in sequence.
Coating an oxygen barrier layer: the following oxygen barrier layer solution was extrusion coated on the thermosensitive layer obtained above, and then dried at 110℃for 60 seconds. 10mg/dm2 of dry coating weight (parts by weight of the components) was obtained.
Oxygen barrier layer formula (weight portions of each component)
Polyvinyl alcohol PVA-205 (Japanese colali) 17
Polyvinylpyrrolidone PVPK30 (BASF Germany) 3
Emulsifier OP-10 (Hanm Germany) 0.45
Deionized water 480
Application detection:
1. Dot reduction: the plate is exposed on a Kodak all-victorious thermosensitive CTP plate making machine with energy of 120mJ/cm < 2 >, whether 1% -99% of net points can be reproduced, 1% -99% is optimal, 2% -99% is repeated, 3% -98% is repeated, and the like is tested. The properties are shown in Table 1;
2. Contrast Δe1: the plate material is exposed on a Kodak all-victorious thermosensitive CTP plate making machine with the energy of 120mJ/cm < 2 >, the density difference between 100% of the field exposure density and the unexposed position is tested, the larger the contrast delta E1 is, the higher the visual identification degree of the image is, and the automatic identification degree of the image cross line after scanning exposure is higher by a printer computer system. The properties are shown in Table 1;
3. Color difference Δe2: the plate material is exposed on a Kodak all-victorious thermosensitive CTP plate making machine with energy of 160mJ/cm2 and 80mJ/cm2, the density difference of different exposure amounts of the black ink of the printing product and 100% of the solid field is tested, the smaller the chromatic aberration delta E2 is, the larger the exposure latitude of the plate material is, and the color uniformity of the exposed printing products of different types of exposure machines is better. The properties are shown in Table 1;
4. And (3) water display time: the plate is exposed on a Kodak all-victorious thermosensitive CTP plate making machine with energy of 120mJ/cm < 2 >, and the time (unit: seconds) for removing the unexposed pattern layer by water development at 25 ℃ is tested, so that the shorter the water development time is, the better the low chemical development property of the plate is. The properties are shown in Table 1;
5. Number of paper passes: the plate is exposed on a Kodak all-victorious thermosensitive CTP plate making machine with the energy of 120mJ/cm < 2 >, directly put on a printer, developed under the action of fountain solution, and the paper is taken to remove the unexposed pattern layer, and the number of paper (unit: sheets) consumed before the printing product is tested normally is smaller, so that the better the on-press development performance of the plate is indicated. The properties are shown in Table 1;
6. Print resistance: the plate material is exposed on a Kodak all-victorious thermosensitive CTP plate making machine with the energy of 120mJ/cm <2 >, printed matters are printed on a four-color rotary printing machine of North China, the number (unit: ten thousand prints) of printable normal printed matters is tested, and the higher the number of the normal printed matters is, the better the plate material quality is. The properties are shown in Table 1;
The detection application results of the table 1 show that compared with other environment-friendly thermosensitive plates, the environment-friendly thermosensitive plate designed by the invention improves the sensitivity of the plate material and improves the dot quality of the plate material through a cationic polymerization and urethanization reaction double imaging mechanism; the thermosetting high-wear-resistance urethane bond net-shaped crosslinking structure is introduced through the crosslinking agent, so that the printing force of the plate is improved; the problem of uniformity of color reproduction of an image layer is improved by improving exposure latitude; the plate making contrast of the plate is improved by selecting the thermochromic dye with a special structure, so that the problem of automatic plate identification by a computer is solved; the plate material has a hydroxyethylacrylamide hydrophilic unit, can realize water development or on-press development, and is a green and environment-friendly thermosensitive plate.
Table 1 version of the application Performance Table
While only the preferred embodiments of the present invention have been described above, the scope of the present invention is not limited thereto, and it should be noted that equivalents and modifications, variations and improvements made according to the technical solution of the present invention and the inventive concept thereof, as well as those skilled in the art, should be considered as the scope of the present invention, without departing from the general inventive concept thereof.
Claims (7)
1. A crosslinking agent characterized by: the structure is as follows:
。
2. The crosslinking agent of claim 1, wherein: the preparation raw materials comprise dicyclohexylmethane-4, 4' -diisocyanate, dibutyltin dilaurate, ethyl-3-oxabutyl cyclomethanol and epsilon-caprolactam.
3. The method for producing a crosslinking agent according to claim 1, wherein: dicyclohexylmethane-4, 4' -diisocyanate, dibutyltin dilaurate and solvent are heated to 35-80 ℃, ethyl-3-oxabutyl cyclomethanol is added dropwise for reaction, epsilon-caprolactam is added for reaction until the peak at the reactive isocyanate group 2275 is detected to disappear by infrared spectrum, and a solution containing a cross-linking agent is obtained.
4. A method of preparing a crosslinker as claimed in claim 3, characterized in that: the solvent is at least one of dimethylformamide, dimethylacetamide, acetone, butanone, 1, 4-butyrolactone and ethyl acetate.
5. The method for producing a crosslinking agent according to claim 4, wherein: dicyclohexylmethane-4, 4' -diisocyanate, dibutyltin dilaurate and dimethylacetamide are heated to 45-65 ℃, ethyl-3-oxabutyl cyclomethanol is added dropwise for reaction for 0.5-2 hours, epsilon-caprolactam is then added for reaction for 10-30 minutes, and the reaction is carried out in an ice water bath for 12-48 hours until the peak at the 2275 position of the active isocyanate group is detected by infrared spectrum to obtain a dimethylformamide solution containing a cross-linking agent.
6. A method of preparing a crosslinker as claimed in claim 3, characterized in that: a four-necked flask with a temperature-controlled heating, mechanical stirring, condensing reflux and drying tube of 1000 ml was charged with 262.3g of dicyclohexylmethane-4, 4' -diisocyanate, 3g of dibutyltin dilaurate, 491.7g of dimethylacetamide, and then heated to 50℃to dropwise add 116.2g of 3-ethyl-3-oxetanyl-methanol for 30 minutes, followed by a reaction for 1 hour, followed by 113.2g of ε -caprolactam, and then reacted for 20 minutes in an ice water bath for 48 hours until the disappearance of the peak at the reactive isocyanate group 2275 was detected by infrared spectroscopy, to give a dimethylformamide solution of the crosslinking agent of claim 1 having a solid content of 50%.
7. A heat-sensitive plate comprising the crosslinking agent of claim 1 or 2 or the crosslinking agent produced by the production method of any one of claims 3 to 6.
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| WO1999011458A1 (en) * | 1997-09-02 | 1999-03-11 | Kodak Polychrome Graphics Llc | Thermal lithographic printing plates |
| CN103879168A (en) * | 2012-12-21 | 2014-06-25 | 乐凯华光印刷科技有限公司 | Thermosensitive plate with long printing stroke |
| CN105372935A (en) * | 2014-08-29 | 2016-03-02 | 乐凯华光印刷科技有限公司 | Processless thermal sensitive plate used for direct printing on printer |
| CN109752921A (en) * | 2017-11-08 | 2019-05-14 | 乐凯华光印刷科技有限公司 | A kind of negative image lithographic precursor and the method that sensitive lithographic plate is prepared by it |
| CN110845692A (en) * | 2019-10-17 | 2020-02-28 | 江西科技师范大学 | High-hardness thermosetting self-repairing polyurethane and preparation method thereof |
| CN111103759A (en) * | 2018-10-26 | 2020-05-05 | 乐凯华光印刷科技有限公司 | Low-chemical-treatment thermosensitive plate and preparation method thereof |
| CN112521548A (en) * | 2020-12-01 | 2021-03-19 | 北京印刷学院 | High-temperature cross-linkable water-soluble resin, preparation method thereof and chemical-treatment-free negative thermosensitive CTP plate coating |
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2021
- 2021-11-05 CN CN202111303770.XA patent/CN113831329B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999011458A1 (en) * | 1997-09-02 | 1999-03-11 | Kodak Polychrome Graphics Llc | Thermal lithographic printing plates |
| CN103879168A (en) * | 2012-12-21 | 2014-06-25 | 乐凯华光印刷科技有限公司 | Thermosensitive plate with long printing stroke |
| CN105372935A (en) * | 2014-08-29 | 2016-03-02 | 乐凯华光印刷科技有限公司 | Processless thermal sensitive plate used for direct printing on printer |
| CN109752921A (en) * | 2017-11-08 | 2019-05-14 | 乐凯华光印刷科技有限公司 | A kind of negative image lithographic precursor and the method that sensitive lithographic plate is prepared by it |
| CN111103759A (en) * | 2018-10-26 | 2020-05-05 | 乐凯华光印刷科技有限公司 | Low-chemical-treatment thermosensitive plate and preparation method thereof |
| CN110845692A (en) * | 2019-10-17 | 2020-02-28 | 江西科技师范大学 | High-hardness thermosetting self-repairing polyurethane and preparation method thereof |
| CN112521548A (en) * | 2020-12-01 | 2021-03-19 | 北京印刷学院 | High-temperature cross-linkable water-soluble resin, preparation method thereof and chemical-treatment-free negative thermosensitive CTP plate coating |
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