CN104742557B - A kind of aqueous developable exempts from chemical treatment temperature-sensitive version and preparation method thereof - Google Patents
A kind of aqueous developable exempts from chemical treatment temperature-sensitive version and preparation method thereof Download PDFInfo
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Abstract
Exempt from chemical treatment temperature-sensitive version and preparation method thereof the invention discloses a kind of aqueous developable, and in particular to cationic crosslinked and radical polymerization can occur simultaneously for one kind, the aqueous developable of environmental protection exempts from chemical treatment temperature-sensitive version and preparation method thereof.The technical problem to be solved be it is existing exempt from chemical treatment heat-sensitive CTP plate technology present in plate water development ability and Nai Yin abilities.The present invention includes support, heat-sensitive layer and protective layer, and described heat-sensitive layer includes the raw material of following weight parts meter：Water soluble thermo-crosslinked 30 70 parts of copolymer, 10 50 parts of the performed polymer containing hydrophilic group, 10 30 parts of polyfunctional monomer, 1 20 parts of cationic initiator, 1 20 parts of infrared light radiation absorbing dye., can directly water development, imaging contrast height, the inspection version before being available on the machine, and can obtain high pressrun after with infrared laser scanning imagery using the present invention after such technical scheme.
Description
Technical field
The present invention relates to lithography technique field, and in particular to a kind of aqueous developable exempts from chemical treatment temperature-sensitive version and its system
Make method.
Background technology
Lithography technique moves towards CTP comprehensively from traditional laser photo film copy PS platemaking technologies
Technology（Abbreviation CTP technologies）, CTP plates also gradually popularize.CTP plates species is a lot, and that compares popularization includes silver salt s transfer CTP
Plate, UV-CTP editions, purple laser polymerization CTP plates, thermal CTP plate material etc..Wherein most popular is thermal CTP plate material.
CTP plate-making technologies needs one, come the process developed, exist with the developer solution containing a variety of toxic organic compounds or highly basic
Poisonous and harmful liquid waste processing and bring environmental problem.At present, it is generation that exploitation new generation of green, environmental protection, which exempt to be chemically treated CTP editions,
The focus of boundary's plate exploitation.
Exploitation green, environmental protection exempt from chemical treatment CTP platemaking technologies route a lot, can be divided into thermal ablation technology, polarity and turn technology
And hot-melt technology.
Thermal ablation technology plate uses aluminum plate foundation or polyester base, and plate is prepared using plasma metal deposition technique.But burn
There are scrap problems in erosion plate.Presstek companies have delivered the ablation plate with sandwich, solve ablation residue and ask
Topic.Agfa Corp. develops the ablation technology with deposited silver layer without processing CTP editions, and the plate is by the branch with water-wetted surface
Hold body（Aluminium, PET）, can be ablated metal deposition layer and crosslinking hydrophobic layer constitute.Metal deposition layer is to utilize metal deposit skill
The metal film of art formation, the metal can be silver, titanium etc..Hydrophobic layer is crosslinked by radiation or heat cure, unsaturated monomer is crosslinked,
Cured layer can be cross-linked to form by heat-sensitive resin, or can be obtained by feeling the processing of fat liquid.Infrared laser power causes in silver layer
Argent grain occur the change of surface tension, form fluffy Argent grain, remain on plate surface, thus with vacuum suction or
Liquid is easy to remove residue, exposes aluminium plate water-wetted surface formation hydrophilic area, and unexposed cross-linked layer does not dissolve in liquid, forms parent
Oily area.
Polarity conversion technology：Plate is made up of support and thermographic layer.Thermographic layer changes agent and heat containing photo-thermal
Quick convertible polymer（Such as poly- oxinane methacrylate, with aryldiazosulphonate base ethylene copolymer）.Using heat
Quick convertible polymer formation thermo-sensitive material.Before imaging, heat-sensitive layer is dissolved in the aqueous solution.During imaging, infrared light radiation absorbing dye
Laser energy is absorbed, the thermally-induced diazo of generation is decomposed, make to be exposed temperature-sensitive copolymer and be changed into hydrophobic from hydrophilic, so as to be formed
Oleophylic area.And unexposed area temperature-sensitive copolymer is still dissolved in water, so as to form hydrophilic area.Restricting the factor of this technology development is still
Printability.Its ink part is all medicine film coating, and printing control and pressrun are realized real extensive all by severely restricts
Commercialization application also has relatively large distance.
Hot-melt technology：Laser energy is converted into heat energy by thermographic mid-infrared light radiation absorbing dye, and the heat of generation makes
The temperature for the thermoplastic polymer particles being dispersed in crosslinked hydrophilic layer is higher than its gel humidity, causes thermoplastic polymer particles
Generation agglutinating reaction, exposure region becomes hydrophobic oleophilic oil by hydrophily.And unexposed area is still dissolved in the aqueous solution of PH >=4, formed
Hydrophilic area.Its printing plate blank parts is frosted and the aluminium base after oxidation processes, rather than medicine film coating, printability and trade edition
Material does not have any difference.
Exempt from processing temperature-sensitive version to be included in machine treatment technology and exempt from chemical treatment method.
In machine treatment technology, its principle is：Planographic printing plate material is precoated after by the scanning plate-making of CTP platemaking machine, it is used to print
The unnecessary coating at the blank position of brush in the presence of damping water and ink on the printer by being removed, and unnecessary coating is gone
Walked after removing by transferring paper tape, blank position is hydrophilic aluminum substrate, this mode realizes lithography process without emissions
Environmentally friendly purpose.But it is due to directly to be printed on the machine after such plate exposes, it has not been convenient to aobvious with developing machine as traditional CT P plates
Movie queen carries out the detection before upper machine to the image on plate, in order to before printing machine is lockd up detection carry out image detection and
Various color versions are recognized when locing up on printing machine, prevents that the phenomenon for printing image error and wrongly installed color version position from occurring, there is certain
Use limitation.
Another way claims " exempting from chemical treatment " technology.Exempt from chemical treatment temperature-sensitive version skill by representative of aqueous developable technology
Art, the advantage of this mode is both to have realized the effect for comparing environment protection emission, while can also be as conventional CTP plates flat
Printing plate carries out the correction of site before being printed on the machine, in order to avoid become blind version on sensitive lithographic plate after machine again.
Chemical treatment CTP editions is exempted from exploitation, and one of key technology is the plate precursor i.e. exploitation of function organic composition.
EP0980754 describes carboxyl decarboxylation and realizes hydrophilic-hydrophobic conversion techniques, but phase in version compound molecular weight is too big, energy threshold
Become big, decarboxylation is difficult, so the technology plate pressrun is poor.WO94/23954 describes a kind of microcapsules hot-melt technology, laser
Hot melt destroys microcapsules, and hydrophilic substance destruction switchs to hydrophobic, but damaged thing easily causes printing blank space pollution；US4004924
The mixture of a kind of thermoplastic hydrophobic's particle and hydrophilic adhesive is introduced, but intolerant to print；Ai Kefa EP 2006-5-24
06114475.4 introduces a kind of semicontinuous emulsion method manufacture styrene, acrylonitrile emulsion thermoplastic granulates, can realize hot melt, but not
Hydrophilic radical containing self-emulsifying, Grain size controlling technical requirements are high, and emulsification stability of emulsion is poor, need to add anti-micro- raw agent, develop
When need to add the material assistances such as exhibiting high surface active material and developing rubber development, produce a large amount of development waste liquids；Kodak US 2005-
8-3 11/196,124, a kind of hydrophilic binding agent is introduced, molecule is one-dimensional linear structure, and pressrun is not high；Kodak US
2006-7-27 11/494,235 introduces one kind and contains hydrophilic group and side chain containing allyl ester, is by carboxyl side group and allyl halide
Compound condensation reaction under alkali effect is formed, but side reaction by-products are more, post processing trouble, and hydrophily is poor, and ester group is still
Intolerant to print.
At present, further improve aqueous developable to exempt to be chemically treated the performance of heat-sensitive CTP plate, the water for particularly improving plate shows
Image ability and Nai Yin abilities are that water development exempts to be chemically treated the focus of thermal CTP plate material exploitation.
The content of the invention
The technical problem to be solved in the present invention be it is existing exempt from chemical treatment heat-sensitive CTP plate technology present in plate water development
There is provided one kind cationic crosslinked and radical polymerization, the aqueous developable of environmental protection can occur for ability and Nai Yin abilities simultaneously
Exempt from chemical treatment temperature-sensitive version and preparation method thereof.
To achieve the above object, the present invention uses following technical proposals：A kind of aqueous developable exempts from chemical treatment temperature-sensitive version, it
Including support, heat-sensitive layer and protective layer, described heat-sensitive layer includes the raw material of following weight parts meter：Water soluble thermo-crosslinked copolymerization
It is 30-70 parts of thing, 10-50 parts of the performed polymer containing hydrophilic group, 10-30 parts of polyfunctional monomer, 1-20 parts of cationic initiator, infrared
1-20 parts of light absorption dyestuff.
Described heat-sensitive layer includes the raw material of following weight parts meter：Water soluble thermo-crosslinked copolymer 40-60 parts, containing hydrophilic group
20-40 parts of performed polymer, 15-20 parts of polyfunctional monomer, 5-15 parts of cationic initiator, infrared light radiation absorbing dye 5-15
Part.
Described water soluble thermo-crosslinked copolymer has following structure:
Wherein, R1, R2, R4 are H atom or methyl；R3 isOrR5 be O atom or
OCH2CH2NHCOO, n are 20-60 integer；A, b, c, d are the parts by weight of correspondence copolymerization units, and parts by weight shared by a are 40-70
Part, parts by weight shared by b are 10-30 parts, and parts by weight shared by c are 10-30 parts, and parts by weight shared by d are 10-30 parts.
The described performed polymer containing hydrophilic group has following structure:
Described polyfunctional monomer is polyfunctional group acrylic monomer or polyfunctional group polyurethane acroleic acid class monomer.
Described cationic initiator is salt compounded of iodine, one kind of sulfosalt or at least two；Cationic initiator is thermally decomposed
Temperature is 150-200 DEG C.
Described infrared light radiation absorbing dye is cyanine dyes of the absworption peak in 750-850nm.
Described heat-sensitive layer coating dry weight is 8-15mg/dm2, described protective layer dry weight is 5-20mg/dm2。
A kind of aqueous developable exempts from the preparation method for being chemically treated temperature-sensitive version, it is characterised in that：It comprises the following steps：（1）
Handle aluminum substrate support；(2) it is coated with heat-sensitive layer on aluminum substrate support after treatment；（3）Coating on heat-sensitive layer is protected
Sheath.
Described processing aluminum substrate support is included to the electrolyzing and coarsening of aluminum substrate support and anodic oxidation and progress
Sealing pores, after processing aluminum substrate support center line average boldness be 0.4-0.6 μm.
Cationic crosslinked and radical polymerization, environmental protection, sensitivity height, site reproducibility can occur simultaneously for the present invention
It is good, can directly water development, imaging contrast height, the inspection version before being available on the machine, and can obtain high after with infrared laser scanning imagery
Pressrun.With dual imaging capability, cationic crosslinked and radical polymerization can be realized simultaneously.Laser thermal energy passes through infrared light
Radiation absorbing dye is by energy transfer to cationic initiator, and cationic initiator produces heterolytic fission and homolysis, heterolytic fission release sun from
Son, makes the epoxy radicals cross-linked polymeric in water soluble thermo-crosslinked copolymer, while the free radical that homolysis is produced makes containing the pre- of hydrophilic group
Radical polymerization occurs for aggressiveness and polyfunctional monomer, realizes dual thermographic, with the crosslinking of single epoxy radicals or radical polymerization
Conjunction is compared, and improves the imaging capability and pressrun of plate；Plate contains two kinds of hydrophilic row functional compounds, water soluble thermo-crosslinked
Copolymer contains esterification suspension polyether-based, and the performed polymer containing hydrophilic group contains bis-phenol structure carboxyl, and both hydrophilic groups all have
Very high space stretching, with very strong hydrophily, improves the water development ability of plate.Using thermosensitive CTP platemaking machine
, can direct water development after scan exposure.
Embodiment
A kind of aqueous developable exempts from chemical treatment temperature-sensitive version, and it includes support, heat-sensitive layer and protective layer, described heat-sensitive layer
Include the raw material of following weight parts meter：Water soluble thermo-crosslinked copolymer 30-70 parts, 10-50 parts of the performed polymer containing hydrophilic group, many officials
Can 10-30 parts of single group body, 1-20 parts of cationic initiator, 1-20 parts of infrared light radiation absorbing dye.
Described heat-sensitive layer includes the raw material of following weight parts meter：Water soluble thermo-crosslinked copolymer 40-60 parts, containing hydrophilic group
20-40 parts of performed polymer, 15-20 parts of polyfunctional monomer, 5-15 parts of cationic initiator, infrared light radiation absorbing dye 5-15
Part.
Described water soluble thermo-crosslinked copolymer has following structure:
Wherein, R1, R2, R4 are H atom or methyl；R3 isOrR5 be O atom or
OCH2CH2NHCOO, n are 20-60 integer；A, b, c, d are the parts by weight of correspondence copolymerization units, and parts by weight shared by a are 40-70
Part, parts by weight shared by b are 10-30 parts, and parts by weight shared by c are 10-30 parts, and parts by weight shared by d are 10-30 parts.
A kind of Thermal sensitive plate is designed, what is considered first is to need a kind of important bonding in the heat-sensitive layer of plate, heat-sensitive layer
Agent is feature film-forming resin, feature film-forming resin can be dried ensureing coating fluid after film forming, heat-sensitive layer is attached to support
On body.Binding agent can be solution state or emulsion state.Contain functional group on feature film-forming resin, undertake
Specific function is acted on, and containing water-soluble heat cross-linking copolymer of the present invention is exactly such binding agent.
Most of temperature-sensitive version functional resins all devise thermoplastic styrene construction unit on resin structure, of the invention
Water soluble thermo-crosslinked copolymer also construction unit containing thermoplastic styrene.It is well known that styrol structural unit has well
Lipophile, thermoplasticity, glass transition temperature are higher, and styrol copolymer has as chemical treatment heat-sensitive CTP plate binding agent is exempted from
Heated portion is easier to arrange more close between hot melt, molecule, and thermal imagery part is more firm, and good rigidity, energy
Increase the advantage of plate pressrun.The multiple copolymer of the present invention is synthesized, styrenic interpolymerized units are in water soluble thermo-crosslinked copolymerization
Parts by weight in thing are 40-70 parts.
A kind of CTP editions binding agent is designed, it is necessary to select outstanding hydrophobic segment.Cyano group is the outstanding hydrophobic group of comparison
Group.The good lipophile of the present invention introduces hydrophobic side chain cyano group, and water soluble thermo-crosslinked copolymer is introduced after hydrophobic side chain cyano group,
There is good pliability, drug resistance and hydrophobicity as binding agent thermal polymerization imaging moiety.The multiple copolymer of the present invention draws
The method for entering hydrophobic side chain radical nitrile is the vinyl component construction unit that side chain nitrile containing base is devised in copolymerization component, preferably third
Alkene nitrile or methacrylonitrile or their mixture.The multiple copolymer of the present invention is synthesized, (methyl) acrylonitrile compolymer unit exists
Parts by weight in water soluble thermo-crosslinked copolymer are 10-30 parts.
The plate that the present invention is designed has cationic crosslinked ability, and infrared laser thermal energy passes through infrared light absorption
Dyestuff is by energy transfer to cationic initiator, and cationic initiator produces heterolytic fission and homolysis, and heterolytic fission is released cation, made water-soluble
Epoxy radicals cross-linked polymeric in property heat cross-linking copolymer.The water soluble thermo-crosslinked copolymer of the present invention is devised in copolymerization component to be contained
The copolymerization units of side chain epoxy based structures, realize that resin side chain hangs epoxy radicals, the present invention is in water soluble thermo-crosslinked copolymer knot
Side chain epoxy, from the acrylic monomer containing epoxy radicals as copolymerization units, the acrylic compounds containing epoxy radicals are introduced in structure chain
Monomer has a lot, such as glycidyl acrylate, GMA, 3,4- expoxycyclohexyls acrylate,
3,4- epoxycyclohexylmethyl acrylate etc., the present invention preferably acrylic monomer containing epoxy radicals, specific example is such as
Under：
Parts by weight of the copolymerization units of the based structures of epoxy containing side chain in water soluble thermo-crosslinked copolymer are 10-30 parts.
As CTP editions hydrophilic agglomerants of chemical treatment are exempted from, water soluble thermo-crosslinked copolymer of the invention contains hydrophilic knot
After structure unit, infrared laser scanning imagery, heat-sensitive layer molecular weight drastically becomes big, makes coating more firm, the painting after LASER HEAT exposure
Layer is difficult to be removed by water and ink；In the unnecessary coating at unexposed blank position due to exist water soluble thermo-crosslinked copolymer and
It is hydrophilic aluminium plate to expose blank position after performed polymer containing hydrophilic group, it is easy to removed by water, unnecessary coating removal
Base, realizes environmentally friendly purpose of the lithography process without emissions.The water soluble thermo-crosslinked copolymer of the present invention is set in copolymerization component
Polyethers hydrophilic structural unit, side chain suspension polyether-based, including esterification branched polyether and urethane branched polyether, specific example are counted
It is as follows（It is not limited only to this）：
Parts by weight of the copolymerization units of the hydrophilic-structure containing branched polyether in water soluble thermo-crosslinked copolymer are 10-30 parts.
Water soluble thermo-crosslinked copolymer of the present invention is synthesized using solution or the method for emulsion copolymerization, copolyreaction can
Select random copolymerization or block copolymerization, preferably random copolymerization.The initiator of polymerization include peroxide such as di-tert-butyl peroxide,
Benzoyl peroxide, persulfate such as potassium peroxydisulfate, Ammonium Persulfate 98.5, azo-compound such as azodiisobutyronitrile etc., copolymerization
The preferred polymerisation in solution of mode.
Available reaction dissolvent have water, methanol, ethanol, normal propyl alcohol, isopropanol, butanol, acetone, MEK, cyclohexanone,
Ethyl acetate, butyl acetate, tetrahydrofuran, Isosorbide-5-Nitrae-dioxane, DMF, dimethylacetylamide acetone, first
Base ethyl ketone, hexamethylene, ethylene dichloride, toluene, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, glycol dimethyl ether, propane diols first
Ether, propylene-glycol ethyl ether, acetylacetone,2,4-pentanedione, DAA, ethylene glycol monomethyl ether acetate, ethyl cellosolve acetate, ethylene glycol isopropyl
Ether, butyl glycol ether acetic acid esters, 3- methoxypropanols, methoxymethoxy ethanol, diethylene glycol dimethyl ether, diethylene glycol ether,
Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol methyl ether acetate, propylene-glycol ethyl ether acetic acid esters, dimethyl sulfoxide, breast
Sour methyl esters and ethyl lactate etc., or their mixture.Preferred 40-100 DEG C of copolyreaction temperature, optimal is 60-90 DEG C.
Water soluble thermo-crosslinked copolymer weight average molecular weight of the present invention is 40000-10000.Glass transition temperature
For 110-130 DEG C.
The parts by weight for the water soluble thermo-crosslinked copolymer that the present invention is designed are 30-70 parts, preferably 40-60 parts.
The present invention improves the water development of plate by adding the performed polymer containing hydrophilic group.Laser thermal energy passes through infrared light
Radiation absorbing dye is by energy transfer to cationic initiator, and cationic initiator produces homolysis, and the free radical of generation makes containing parent
Radical polymerization occurs for water base performed polymer and polyfunctional monomer, realizes free radical thermographic.Performed polymer containing hydrophilic group
Have a lot, such as polyether-based acrylic compounds performed polymer, amide groups acrylic compounds performed polymer, sulfoamido acrylic compounds performed polymer, in
Esters acrylic compounds performed polymer and polyurethanes performed polymer etc..Performed polymer of the present invention containing hydrophilic group has as follows
Structure:
It has it is several a little：1st, containing polyurethane-base-NHCOO, heat-sensitive layer has the spy of polyurethane after radical polymerization
The advantage of property such as pliability, solvent resistance, wearability；2nd, the pi-allyl containing the high spatial free degree, activity is higher；3rd, containing height
The carboxyl base of spatial degrees of freedom, hydrophily is more preferable；4th, class bis-phenol structure, film layer rigidity more preferably, improves wearability after polymerization.
The parts by weight of performed polymer containing hydrophilic group are 10-50 parts, preferably 20-40 parts.
The present invention is containing two kinds of hydrophily functional compounds, and water soluble thermo-crosslinked copolymer contains esterification suspension polyether-based,
Performed polymer containing hydrophilic group contains bis-phenol structure carboxyl, and both hydrophilic groups all have very high space stretching, with very strong
Hydrophily, improve the water development ability of plate.
Described polyfunctional monomer is polyfunctional group acrylic monomer or polyfunctional group polyurethane acroleic acid class monomer.
The plate that may occur from being polymerize by base can use various types of monomers, such as：Monofunctional monomers, there is (methyl) acrylate
Such as ethyl acrylate, butyl acrylate, allyl acrylate；Polyfunctional monomer, there is diacrylate, 1,6- hexylene glycols two
Acrylate, pentaerythritol triacrylate and tetraacrylate, 1,3,5- tri--(2- acrylyl oxy-ethyls) isocyanuric acid esters,
Hydroxypropyl glycerine base triacrylate, ethoxy trimethylolpropane trimethacrylate, polyethylene glycol dimethacrylate etc.；
Isocyanate group monomer, has 2- methacryloyloxyethyls acetoacetic ester and dimethyl-m-isopropenyl benzyl isocyanate ester etc., preferably makes
Use polyfunctional monomer.Polyfunctional monomer in heat-sensitive layer of the present invention is selected from polyfunctional group acrylic monomer or many
Functional polyurethane acrylic monomer.The parts by weight of polyfunctional monomer are 10~30 parts, preferably 15~20 parts.
Described cationic initiator is salt compounded of iodine, one kind of sulfosalt or at least two；Cationic initiator is thermally decomposed
Temperature is 150-200 DEG C.Salt compounded of iodine, sulfosalt can be mixed with arbitrary proportion.Sheet material has dual imaging capability, and sun can be achieved
Ionomer and radical polymerization.Laser thermal energy is triggered energy transfer to cation by infrared light radiation absorbing dye
Agent, cationic initiator produces heterolytic fission and homolysis, and heterolytic fission releases cation, hands over the epoxy radicals in water soluble thermo-crosslinked copolymer
Connection polymerization, while the free radical that homolysis is produced makes performed polymer and polyfunctional monomer containing hydrophilic group occur radical polymerization, it is real
Existing dual thermographic, compared with the crosslinking of single epoxy radicals or radical polymerization, improves plate pressrun.Sun of the present invention
Ionic initiator is selected from salt, such as sulfosalt, salt compounded of iodine.Suitable salt include the sub- maple salt of sulfosalt, oxygen, oxygen sulfonium salt,
Sulfoxide salt, diazol and halogen such as iodine anchor salt etc..The instantiation of suitable salt is such as：Chlorinated diphenyl base salt compounded of iodine, six
Fluorophosphoric acid diphenyl iodnium, hexafluoro-antimonic acid diphenyl iodnium, hexafluoro-antimonic acid [4- [(2- hydroxy-tetradecyls base-epoxide] benzene
Base] phenyl salt compounded of iodine, tetrafluoro boric acid triphenylsulfonium salt compounded of iodine, octyl sulfate triphenylsulfonium salt compounded of iodine, hexafluorophosphoric acid -2- methoxies
Base -4- aminophenyl diazoniums salt, hexafluoro-antimonic acid Phenoxyphenyl diazol etc..Cationic initiator of the present invention is selected from can
Homolysis and salt compounded of iodine, the one or more of sulfosalt of heterolytic fission occur simultaneously.Its heat decomposition temperature is at 150-200 DEG C.Cation
The parts by weight of initiator are 1~20 part, preferably 5~15 parts.
Described infrared light radiation absorbing dye is cyanine dyes of the absworption peak in 750-850nm.In heat-sensitive layer of the present invention
Component infrared light radiation absorbing dye mainly plays energy transfer, and the heat of infrared laser is contaminated by infrared light absorption
Laser energy is passed to cationic initiator by material, and cationic initiator produces heterolytic fission and homolysis, and heterolytic fission releases cation, makes water
Epoxy radicals cross-linked polymeric in dissolubility heat cross-linking copolymer, while the free radical that homolysis is produced makes performed polymer containing hydrophilic group and many
Radical polymerization occurs for monomer, realizes dual thermographic, compared with the crosslinking of single epoxy radicals or radical polymerization, carries
High plate pressrun.
The maximum absorption wavelength scope containing infrared absorbing compounds is 750-1100nm in temperature-sensitive version heat-sensitive layer, selected from carbon
Black, azo dyes, triaryl amine dyestuff, indoline dye, oxonol dye, cyanine dye, merocyanine dye, indole cyanine dyes, phthalein
Cyanine dyes, polythiophene dye, pyrazoline azo dye, oxazine dyes, naphthoquinone dyestuff, anthraquinone dye, quinoneimine dye, methine
Dyestuff, porphyrin dye etc..Component contained by negative graph photosensitive composition of the present invention：Infrared light radiation absorbing dye is absorption maximum model
Preferably 750-850nm cyanine dyes is enclosed, the parts by weight of infrared light radiation absorbing dye are 1~20 part, preferably 5~15 parts.
Described heat-sensitive layer coating dry weight is 8-15mg/dm2, and described protective layer dry weight is 5-20mg/dm2.
A kind of aqueous developable exempts from the preparation method for being chemically treated temperature-sensitive version, it is characterised in that：It comprises the following steps：（1）
Handle aluminum substrate support；(2) it is coated with heat-sensitive layer on aluminum substrate support after treatment；（3）Coating on heat-sensitive layer is protected
Sheath.
Described processing aluminum substrate support is included to the electrolyzing and coarsening of aluminum substrate support and anodic oxidation and progress
Sealing pores, after processing aluminum substrate support center line average boldness be 0.4-0.6 μm.
Temperature-sensitive layer composition of the present invention need to be applied on temperature-sensitive plate support, and the support of temperature-sensitive version includes paper mold base, gathered
Ester group, rubber version base, composite version base and metal version base such as copperplate base, aluminum substrate etc..Temperature-sensitive version selected by the present invention
Support is aluminum substrate, a kind of aluminum substrate of process special process processing.
Aluminum substrate handling process：Version base used by the present invention is by electrolyzing and coarsening and anodic oxidation and carries out sealing pores
Aluminum substrate afterwards, its center line average boldness is in 0.4-0.6um.Such version base can be made by the method for various electrolyzing and coarsenings.
Aluminum substrate of the present invention is high-purity aluminium plate, and its aluminium content is preferably more than 99%.Suitable aluminum substrate is (but being not limited only to this):
Iron, which accounts for 0.1%-0.5%, silicon and accounts for 0.03%-0.3%, copper, accounts for 0.003%-0.03%, and titanium accounts for 0.01%-0.l%.Electricity used by electrolyzing and coarsening
Solution liquid can be the aqueous solution of acid, alkali or salt or the aqueous solution containing organic solvent.Wherein, with hydrochloric acid, nitric acid or they
It is preferable that the aqueous solution of salt makees electrolyte.Aluminium plate is placed on 1%-30% NaOH, potassium hydroxide, sodium carbonate, sodium metasilicate first
Deng the aqueous solution in, the chemical attack of 5-250 seconds is carried out at a temperature of 20-80 DEG C.Then in 10%-30% nitric acid or sulfuric acid
In neutralized with 20-70 DEG C of temperature, to remove grey matter.Aluminium plate so Jing Guo cleaning treatment, at a temperature of 10-6O DEG C, is used
Square wave, bench-type ripple or sine wave that positive and negative sexual intercourse mutually changes etc., with 5-100A/dm2Current density, in nitric acid or hydrochloric acid
Electrolyte in electrolysis processing 10-300 seconds.Then, the aluminium plate by electrolysis carries out anodized.Anodic oxidation is generally used
Sulfuric acid process.The concentration of the sulfuric acid used is 5-30%, and current density is 1-15A/dm2, oxidizing temperature is in 20-60 DEG C, oxidization time
For 5-250 seconds, to form 1-10g/m2Oxide-film.The oxide-film so formed generally has higher oxide-film micropore, inhales
Attached ability is stronger, it is easy to adhere to foul.So generally also needing to carry out sealing pores.Sealing pores can use various
Method, is preferred with the 50-80% volumes for reaching closing oxide-film micropore.Finally on the aluminium sheet Jing Guo above-mentioned processing, poly- second is applied
Alkenyl phosphonic acid, thickness is 3mg/m2.
The temperature-sensitive layer composition of the present invention can also include some other necessary auxiliary agents, such as institute's solvent, normal temperature thermal polymerization
Inhibitor, coating colours, surfactant etc..
Solvent is primarily to prepare heat-sensitive layer photosensitive liquid, and preparing heat-sensitive layer photosensitive liquid solvent includes：Acetone, Methylethyl
Ketone, hexamethylene, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, glycol dinitrate
Ether, propylene glycol monomethyl ether, propylene-glycol ethyl ether, acetylacetone,2,4-pentanedione, cyclohexanone, DAA, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether
Acetic acid esters, glycol isopropyl ether, butyl glycol ether acetic acid esters, 3- methoxypropanols, methoxymethoxy ethanol, diethylene glycol first
Ether, diethylene glycol ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol methyl ether acetate, propylene-glycol ethyl ether acetic acid
Ester, N.N- dimethylformamides, dimethyl sulfoxide, methyl lactate and ethyl lactate etc..Solvent can be with pure material form or mixing
Thing form is used.
Normal temperature thermal polymerization inhibitor is the ordinary temperature stability of raising plate in order to prevent that sheet material from polymerizeing at normal temperatures.
Thermal polymerization inhibitor includes：Quinhydrones, NO free radical piperidine alcohols, p methoxy phenol, BHT, 1,2,3,-thrihydroxy-benzene,
Tert-butyl catechol, benzoquinones, 4,4 '-thiobis-(3 methy 6 tert butyl phenol), 2,2 '-di-2-ethylhexylphosphine oxide (4- methyl isophthalic acids 6-
Tert-butyl phenol), and N- nitroso phenylhydroxylamines primary cerium salt etc..
Heat-sensitive layer contains figure layer colouring agent.In order to increase the image density after temperature-sensitive version plate-making, it is easy to temperature-sensitive after plate-making
Version is visually inspected or graphical analysis measuring apparatus measurement plate performance, and figure is added in the temperature-sensitive figure layer of temperature-sensitive version of the present invention
Layer colouring agent.It includes：If crystal violet, ethyl violet, crystal violet, the interior purple of crystallization, Victoria blue, glossy dark green, oil blue, oil yellow, pellet
Bright B, methyl violet, malachite green, methylene blue, triazines etc..
Heat-sensitive layer contains surfactant, can select nonionic surfactant, amphoteric surfactant, is lived containing silicon face
Property agent, fluorine-containing surfactant etc..Such as betaines, glycerol stearate esters, the brown grease class of sorbic acid, polysiloxane-based, poly-
Fluoroalkyl ethers.
As the temperature-sensitive version of the present invention, layer protective layer is applied on heat-sensitive layer, oxygen present in air or other is prevented
The performance of pollutant effect heat-sensitive layer in environment.As the material for protective layer, preferably have water miscible polymer, it is such as poly-
(vinyl alcohol), polyvinylpyrrolidone, acid cellulose derivative, gelatin, gum arabic and poly- (allyl phenol etc..These
Material can be obtained as the main component of protective layer refuses oxygen and development removeability very well.For the specific example of polyvinyl alcohol
For, the compound that 71-100% hydrolysis and molecular weight are 300-2400 can be exemplified as.Specific example has：PVA-105,
PVA-110,PVA-117、PVA-117H.PVA-120,PVA-124.PVA-124H.PVA-CS.PVA-CST,PVA-HC.PVA-
203,PVA-204,PVA-205,PVA-210,PVA-217,PVA-220,PVA-224,PVA-217EE,PVA-217E,PVA-
220E.PVA-224E, PVA-405, PVA-420, PVA-613 etc..The coating weight of protective layer is usually 5- in terms of dry mass
20mg/dm2, preferably 10-15mg/dm2
Generally with the field, oneself knows technology coating (e.g., cutter painting, blade coating, bar painting, roller coat, pressure to the heat-sensitive composition of the present invention
Apply etc.) on aluminum substrate.
With reference to specific embodiment, the present invention is described in detail:
Raw material can be obtained from following company：Styrene St：Han Dynasty in Shandong Province honor Energy Science Co., Ltd；Methacrylonitrile
MAN, acrylonitrile AN：The factory of Tianjin chemical reagent two；C1, C2, C3, C4 example compound：Mitsubishi chemistry；Different polymerization degree shows
Example compound D1, D2, D3, D4：SIGMA companies of Britain；MEK MEK：Japan improves petrochemical industry.Azo-bis-isobutyl cyanide：Good fortune gloomyization
Learn;Benzoyl peroxide BPO:Laiwu health novel agent.
Part I：Water soluble thermo-crosslinked copolymer（Code name P）Synthesize example P01-P10
Embodiment（1）（Water soluble thermo-crosslinked copolymer p 01）
Add in four-hole boiling flasks of the 1000ml with temperature control heating, mechanical agitation, condensing reflux and nitrogen protection device
333.3g MEKs, 10g（10 weight %）Example compound D2 (n about 60), heating stirring is uniform, and 70g is added dropwise at 90 DEG C（70 weights
Measure %）St (styrene), 10g (10 weight %) AN (acrylonitrile), 10g（10 weight %）Example compound C2,0.7g benzoyl peroxide first
Acyl BPO, time for adding 20 minutes, then react 0.3g benzoyl peroxide BPO are added after 7.5 hours, continuation is reacted 12 hours again
After terminate, performance sees attached list 1.
Embodiment（2）（Water soluble thermo-crosslinked copolymer p 02）
Add in four-hole boiling flasks of the 1000ml with temperature control heating, mechanical agitation, condensing reflux and nitrogen protection device
344.8g MEKs, 10g（10 weight %）Example compound D4 (n about 50), heating stirring is uniform, and 60g is added dropwise at 80 DEG C（60 weights
Measure %）St (styrene), 20g (20 weight %) AN (acrylonitrile), 10g（10 weight %）Example compound C3,0.7gAIBN (azo
Bis-isobutyronitrile), time for adding 20 minutes, then react 0.3gAIBN (azodiisobutyronitrile) is added after 7.5 hours, continuation is reacted again
Terminate after 12 hours, performance sees attached list 1.
Embodiment（3）（Water soluble thermo-crosslinked copolymer p 03）
Add in four-hole boiling flasks of the 1000ml with temperature control heating, mechanical agitation, condensing reflux and nitrogen protection device
384.6g MEKs, 10g（10 weight %）Example compound D4 (n about 40), heating stirring is uniform, and 50g is added dropwise at 80 DEG C（50 weights
Measure %）St (styrene), 30g (30 weight %) AN (acrylonitrile), 10g（10 weight %）Example compound C2,0.7gAIBN (azo
Bis-isobutyronitrile), time for adding 20 minutes, then react 0.3gAIBN (azodiisobutyronitrile) is added after 7.5 hours, continuation is reacted again
Terminate after 12 hours, performance sees attached list 1.
Embodiment（4）（Water soluble thermo-crosslinked copolymer p 04）
Add in four-hole boiling flasks of the 1000ml with temperature control heating, mechanical agitation, condensing reflux and nitrogen protection device
416.7g MEKs, 30g（30 weight %）Example compound D2 (n about 20), heating stirring is uniform, and 40g is added dropwise at 80 DEG C（40 weights
Measure %）St (styrene), 10g (10 weight %) AN (acrylonitrile), 20g（20 weight %）Example compound C3,0.7gAIBN (azo
Bis-isobutyronitrile), time for adding 20 minutes, then react 0.3gAIBN (azodiisobutyronitrile) is added after 7.5 hours, continuation is reacted again
Terminate after 12 hours, performance sees attached list 1.
Embodiment（5）（Water soluble thermo-crosslinked copolymer p 05）
Add in four-hole boiling flasks of the 1000ml with temperature control heating, mechanical agitation, condensing reflux and nitrogen protection device
454.5g MEKs, 10g（10 weight %）Example compound D2 (n about 50), heating stirring is uniform, and 60g is added dropwise at 80 DEG C（60 weights
Measure %）St (styrene), 10g (10 weight %) AN (acrylonitrile), 20g（20 weight %）Example compound C2,0.7gAIBN (azo
Bis-isobutyronitrile), time for adding 20 minutes, then react 0.3gAIBN (azodiisobutyronitrile) is added after 7.5 hours, continuation is reacted again
Terminate after 12 hours, performance sees attached list 1.
Embodiment（6）（Water soluble thermo-crosslinked copolymer p 06）
Add 500g in four-hole boiling flasks of the 1000ml with temperature control heating, mechanical agitation, condensing reflux and nitrogen protection device
MEK, 10g（10 weight %）Example compound D4 (n about 40), heating stirring is uniform, and 50g is added dropwise at 80 DEG C（50 weight %）St
(styrene), 10g (10 weight %) AN (acrylonitrile), 30g（30 weight %）Example compound C3, the 0.7g AIBN (isobutyls of azo two
Nitrile), time for adding 20 minutes, then react 0.3gAIBN (azodiisobutyronitrile) is added after 7.5 hours, continuation is reacted 12 hours again
After terminate, performance sees attached list 1.
Embodiment（7）（Water soluble thermo-crosslinked copolymer p 07）
Add in four-hole boiling flasks of the 1000ml with temperature control heating, mechanical agitation, condensing reflux and nitrogen protection device
555.5g MEKs, 30g（30 weight %）Example compound D4 (n about 20), heating stirring is uniform, and 40g is added dropwise at 80 DEG C（40 weights
Measure %）St (styrene), 20g (20 weight %) AN (acrylonitrile), 10g（10 weight %）Example compound C2,0.7g AIBN (azos
Bis-isobutyronitrile), time for adding 20 minutes, then react 0.3g AIBN (azodiisobutyronitrile) are added after 7.5 hours, continue anti-again
Answer and terminate after 12 hours, performance sees attached list 1.
Embodiment（8）（Water soluble thermo-crosslinked copolymer p 08）
Add in four-hole boiling flasks of the 1000ml with temperature control heating, mechanical agitation, condensing reflux and nitrogen protection device
588.2g MEKs, 20g（20 weight %）Example compound D2 (n about 30), heating stirring is uniform, and 60g is added dropwise at 80 DEG C（60 weights
Measure %）St (styrene), 10g (10 weight %) AN (acrylonitrile), 10g（10 weight %）Example compound C3,0.7g AIBN (azos
Bis-isobutyronitrile), time for adding 20 minutes, then react 0.3gAIBN (azodiisobutyronitrile) is added after 7.5 hours, continuation is reacted again
Terminate after 12 hours, performance sees attached list 1.
Embodiment（9）（Water soluble thermo-crosslinked copolymer p 09）
Add in four-hole boiling flasks of the 1000ml with temperature control heating, mechanical agitation, condensing reflux and nitrogen protection device
769.2g MEKs, 30g（30 weight %）Example compound D1 (n about 30), heating stirring is uniform, and 50g is added dropwise at 70 DEG C（50 weights
Measure %）St (styrene), 10g (10 weight %) MAN (methacrylonitrile), 10g（10 weight %）Example compound C1,0.7g AIBN
(azodiisobutyronitrile), time for adding 20 minutes, then react 0.3g AIBN (azodiisobutyronitrile) are added after 7.5 hours, continue
React and terminate after 12 hours again, performance sees attached list 1.
Embodiment（10）（Water soluble thermo-crosslinked copolymer p 10）
Add 1000g in four-hole boiling flasks of the 1500ml with temperature control heating, mechanical agitation, condensing reflux and nitrogen protection device
MEK, 10g（10 weight %）Example compound D3 (n about 60), heating stirring is uniform, and 40g is added dropwise at 60 DEG C（40 weight %）St
(styrene), 30g (30 weight %) MAN (methacrylonitrile), 20g（20 weight %）Example compound C4,0.7g AIBN (azos
Bis-isobutyronitrile), time for adding 20 minutes, then react 0.3g AIBN (azodiisobutyronitrile) are added after 7.5 hours, continue anti-again
Answer and terminate after 12 hours, performance sees attached list 1.
Comparative example 1-5（Synthesize similar Ai Kefa polymer A1-A5）：
Introduced according to Ai Kefa patent EP 2006-5-24 06114475.4, similar Ai Kefa is synthesized with polymerisation in solution hair
Polymer, but polymer is free of hydrophilic radical, polymer architecture：
Basic operation：In four-hole boiling flasks of the 1000ml with temperature control heating, mechanical agitation, condensing reflux and nitrogen protection device
In plus 400 MEKs, 5g lauryl sodium sulfate, 60g is added dropwise at 80 DEG C（60 weight %）ST (styrene), 40g (40 weight %)
AN (acrylonitrile), 0.7g AIBN (azodiisobutyronitrile), time for adding 0.5 hour, then add after reacting 7.5 hours
0.3gAIBN (azodiisobutyronitrile), continuation is reacted terminate after 12 hours again.
Change charge ratio, reaction density, synthesize similar Ai Kefa polymer A1-A5, performance sees attached list 1.
Comparative example 6-10（Synthesize similar Kodak's polymer K1-K5）：
According to Kodak patent US 2005-8-3 11/196, similar Ai Kefa polymer, polymerization are synthesized with polymerisation in solution hair
Thing hydrophilic radical containing change, but without epoxy radicals, polymer architecture：
Basic operation：In four-hole boiling flasks of the 1000ml with temperature control heating, mechanical agitation, condensing reflux and nitrogen protection device
In plus 400g MEKs, 20g is added dropwise at 80 DEG C（0 weight %）ST (styrene), 70g (70 weight %) AN (acrylonitrile),
20g0.7g (20 weight %) PEGMA (polyethoxy methacrylate), AIBN (azodiisobutyronitrile), time for adding 0.5 are small
When, then react 0.3g AIBN (azodiisobutyronitrile) are added after 7.5 hours, continuation is reacted terminate after 12 hours again.
Change charge ratio, reaction density synthesizes similar Kodak's polymer K1-K5, and performance sees attached list 1.
Part II：Performed polymer containing hydrophilic group（Code name M）Synthesis:
Intermediate k1 (is purchased from Ai Kefa speciality chemicals company, commercial disignation v003554)：
Intermediate k2（Purchased from Japanese Showa electrician SDK, commercial disignation Karenz MOI）：
MEK MEK：Japan improves petrochemical industry.
Dibutyl tin laurate：The factory of Tianjin chemical reagent one.
Add in four-hole boiling flasks of the 2000ml with temperature control heating, mechanical agitation, condensing reflux and nitrogen protection device
288.0g intermediate k1,150g MEK MEK, 6.0g dibutyl tin laurates, nitrogen protection, be heated to 60 DEG C dropwise addition
310.0g intermediate k2, time for adding 30 minutes reacts 2 hours, reacts 48 hours, is examined until by infrared spectrum under ice-water bath
Survey peak at active isocyanate base 2275 to disappear, obtain the MEK solution for the target compound M that solid content is 80%.
The following is the implementation example of the present invention, but it is not limited to following instance：
Embodiment 1
The preparation of version base：The A1050 calendering aluminium plates of purity 99.5%, thickness 0.3mm, in 5% sodium hydrate aqueous solution
Etch 20 seconds at 70 DEG C, after being rinsed with flowing water, are neutralized with 1% aqueous solution of nitric acid immediately.Then in 1% aqueous hydrochloric acid solution,
It is roughened 16 seconds with 50A/dm2 current density electrolysis with sine wave alternating current at 40 DEG C.Then at 40 DEG C, with 5% hydroxide
With 10 seconds in sodium water solution.Washing.Finally at 30 DEG C, with 20% aqueous sulfuric acid, with 15A/dm2 current density, anode
Oxidation 20 seconds.Washing.At 80 DEG C sealing pores are carried out with 5% sodium silicate aqueous solution 18 seconds.Washing.Dry.The version so obtained
Base, center line average boldness is 0.5um, oxide-film weight 3.0g/dm2.
Heat-sensitive layer is coated with：Photosensitive liquid in the version base of above-mentioned process hydrophilicity-imparting treatment below extrusion coated, then 100
Dried 60 seconds at DEG C.Obtain 10mg/dm2 dry coating weight.Photosensitive liquid uses following component (each component is by weight)：
Protective layer is coated with：The following protective layer solution of extrusion coated on heat-sensitive layer obtained above, then at 110 DEG C
Dry 60 seconds.Obtain 10mg/dm2 dry coating weight (each component is by weight).
Infrared absorbing dye ADS830 structure is as follows：
The plate so obtained is in the all-victorious thermosensitive CTP platemaking machine of Kodak with 120mJ/cm2Energy be exposed.Its
Performance is listed in table 2 below.
Embodiment 2
Version base, heat-sensitive layer and protective layer are prepared with identical method above.Photosensitive liquid is with component the following：
The plate so obtained is in the all-victorious thermosensitive CTP platemaking machine of Kodak with 120mJ/cm2Energy be exposed.Its
Performance is listed in table 2 below.
Embodiment 3
Version base, heat-sensitive layer and protective layer are prepared with identical method above.Photosensitive liquid is with component the following：
The plate so obtained is in the all-victorious thermosensitive CTP platemaking machine of Kodak with 120mJ/cm2Energy be exposed.Its
Performance is listed in table 2 below.
Embodiment 4
Version base, heat-sensitive layer and protective layer are prepared with identical method above.Photosensitive liquid is with component the following：
The plate so obtained is in the all-victorious thermosensitive CTP platemaking machine of Kodak with 120mJ/cm2Energy be exposed.Its
Performance is listed in table 2 below.
Embodiment 5
Version base, heat-sensitive layer and protective layer are prepared with identical method above.Photosensitive liquid is with component the following：
The plate so obtained is in the all-victorious thermosensitive CTP platemaking machine of Kodak with 120mJ/cm2Energy be exposed.Its
Performance is listed in table 2 below.
Embodiment 6
Version base, heat-sensitive layer and protective layer are prepared with identical method above.Photosensitive liquid is with component the following：
The plate so obtained is in the all-victorious thermosensitive CTP platemaking machine of Kodak with 120mJ/cm2Energy be exposed.Its
Performance is listed in table 2 below.
Embodiment 7
Version base, heat-sensitive layer and protective layer are prepared with identical method above.Photosensitive liquid is with component the following：
The plate so obtained is in the all-victorious thermosensitive CTP platemaking machine of Kodak with 120mJ/cm2Energy be exposed.Its
Performance is listed in table 2 below.
Embodiment 8
Version base, heat-sensitive layer and protective layer are prepared with identical method above.Photosensitive liquid is with component the following：
The plate so obtained is in the all-victorious thermosensitive CTP platemaking machine of Kodak with 120mJ/cm2Energy be exposed.Its
Performance is listed in table 2 below.
Embodiment 9
Version base, heat-sensitive layer and protective layer are prepared with identical method above.Photosensitive liquid is with component the following：
The plate so obtained is in the all-victorious thermosensitive CTP platemaking machine of Kodak with 120mJ/cm2Energy be exposed.Its
Performance is listed in table 2 below.
Embodiment 10
Version base, heat-sensitive layer and protective layer are prepared with identical method above.Photosensitive liquid is with component the following：
The plate so obtained is in the all-victorious thermosensitive CTP platemaking machine of Kodak with 120mJ/cm2Energy be exposed.Its
Performance is listed in table 2 below.
Embodiment 11
Version base, heat-sensitive layer and protective layer are prepared with identical method above.Photosensitive liquid is with component the following：
The plate so obtained is in the all-victorious thermosensitive CTP platemaking machine of Kodak with 120mJ/cm2Energy be exposed.Its
Performance is listed in table 2 below.
Embodiment 12
Version base, heat-sensitive layer and protective layer are prepared with identical method above.Photosensitive liquid is with component the following：
The plate so obtained is in the all-victorious thermosensitive CTP platemaking machine of Kodak with 120mJ/cm2Energy be exposed.Its
Performance is listed in table 2 below.
Embodiment 13
Version base, heat-sensitive layer and protective layer are prepared with identical method above.Photosensitive liquid is with component the following：
The plate so obtained is in the all-victorious thermosensitive CTP platemaking machine of Kodak with 120mJ/cm2Energy be exposed.Its
Performance is listed in table 2 below.
Embodiment 14
Version base, heat-sensitive layer and protective layer are prepared with the identical method of embodiment 1.Simply make the center line average boldness of version base
For 0.4um
The plate so obtained is in the all-victorious thermosensitive CTP platemaking machine of Kodak with 120mJ/cm2Energy be exposed.Its
Performance is listed in table 2 below.
Embodiment 15
Version base, heat-sensitive layer and protective layer are prepared with the identical method of embodiment 1.Simply make the center line average boldness of version base
For 0.6um
The plate so obtained is in the all-victorious thermosensitive CTP platemaking machine of Kodak with 120mJ/cm2Energy be exposed.Its
Performance is listed in table 2 below.
Embodiment 16
Version base, heat-sensitive layer and protective layer are prepared with the identical method of embodiment 1.The dry coating weight for simply making heat-sensitive layer is
8mg/dm2
The plate so obtained is in the all-victorious thermosensitive CTP platemaking machine of Kodak with 120mJ/cm2Energy be exposed.Its
Performance is listed in table 2 below.
Embodiment 17
Version base, heat-sensitive layer and protective layer are prepared with the identical method of embodiment 1.The dry coat weight for simply making heat-sensitive layer is
15mg/dm2
The plate so obtained is in the all-victorious thermosensitive CTP platemaking machine of Kodak with 120mJ/cm2Energy be exposed.Property
It can be listed in table 2 below.
Embodiment 18
Version base, heat-sensitive layer and protective layer are prepared with the identical method of embodiment 1.The dry coat weight for simply making protective layer is
5mg/dm2
The plate so obtained is in the all-victorious thermosensitive CTP platemaking machine of Kodak with 120mJ/cm2Energy be exposed.Its
Performance is listed in table 2 below.
Embodiment 19
Version base, heat-sensitive layer and protective layer are prepared with the identical method of embodiment 1.The dry coat weight for simply making protective layer is
20mg/dm2
The plate so obtained is in the all-victorious thermosensitive CTP platemaking machine of Kodak with 120mJ/cm2Energy be exposed.Its
Performance is listed in table 2 below.
Wherein, embodiment 1-19 water-soluble polymer P1-P10 is water soluble thermo-crosslinked copolymer, and M is containing hydrophilic group
Performed polymer, pentaerythritol triacrylate is polyfunctional monomer, and diaryl hexafluorophosphoric acid salt compounded of iodine is cationic initiator, red
Outer light absorption dyestuff ADS830 be infrared light radiation absorbing dye, NO free radical piperidine alcohols normal temperature thermal polymerization inhibitor,
Alkaline bright blue is figure layer colouring agent, and MEK and 1- methoxy-2-propanols are solvent.
Comparative example 1-5
Version base, heat-sensitive layer and protective layer are prepared with the identical method of embodiment 1.Photosensitive coating fluid uses following component：
The plate so obtained is in the all-victorious thermosensitive CTP platemaking machine of Kodak with 120mJ/cm2Energy be exposed.Its
Performance is listed in table 2 below.
Comparative example 6-10
Version base, heat-sensitive layer and protective layer are prepared with the identical method of embodiment 1.Photosensitive coating fluid uses following component：
The plate so obtained is in the all-victorious thermosensitive CTP platemaking machine of Kodak with 120mJ/cm2Energy be exposed, version
Material performance sees attached list 2.
Shown by the detection application result of subordinate list, compared with radical polymerization mechanism plate, what the present invention was designed can water
Chemical treatment temperature-sensitive version is exempted from development has dual imaging capability, and cationic crosslinked and radical polymerization can be achieved, plate is improved
Imaging capability and pressrun；Performed polymer containing hydrophilic group contains polyurethane-base-NHCOO, and film layer has pliability, solvent resistant
Property, the advantage of wearability；Pi-allyl containing the high spatial free degree, activity is higher, and site reduction is more preferable；Plate contains two kinds of parents
Water row functional compounds, water soluble thermo-crosslinked copolymer contains esterification suspension polyether-based, and the performed polymer containing hydrophilic group contains bis-phenol
Structure carboxyl, both hydrophilic groups all have very high space stretching, and with very strong hydrophily, the water for improving plate shows
Image ability, can be achieved the water development of environmental protection.
Subordinate list 1：Polymer performance table
Subordinate list 2：Plate application performance table
Claims (9)
1. a kind of aqueous developable exempts from chemical treatment temperature-sensitive version, it is characterised in that：It includes support, heat-sensitive layer and protective layer, institute
The heat-sensitive layer stated includes the raw material of following weight parts meter：Water soluble thermo-crosslinked copolymer 30-70 parts, the performed polymer containing hydrophilic group
10-50 parts, 10-30 parts of polyfunctional monomer, 1-20 parts of cationic initiator, 1-20 parts of infrared light radiation absorbing dye；
Described water soluble thermo-crosslinked copolymer has following structure:
Wherein, R1, R2, R4 are H atom or methyl；R3 isOr；R5 be O atom or
OCH2CH2NHCOO, n are 20-60 integer；A, b, c, d are the parts by weight of correspondence copolymerization units, and parts by weight shared by a are 40-70
Part, parts by weight shared by b are 10-30 parts, and parts by weight shared by c are 10-30 parts, and parts by weight shared by d are 10-30 parts.
2. aqueous developable according to claim 1 exempts from chemical treatment temperature-sensitive version, it is characterised in that：Described heat-sensitive layer includes
The raw material of following weight parts meter：Water soluble thermo-crosslinked copolymer 40-60 parts, 20-40 parts of the performed polymer containing hydrophilic group, polyfunctional group
15-20 parts of monomer, 5-15 parts of cationic initiator, 5-15 parts of infrared light radiation absorbing dye.
3. aqueous developable according to claim 1 or 2 exempts from chemical treatment temperature-sensitive version, it is characterised in that：Described containing is hydrophilic
The performed polymer of base has following structure:
。
4. aqueous developable according to claim 1 or 2 exempts from chemical treatment temperature-sensitive version, it is characterised in that：Described is multifunctional
Single group body is polyfunctional group acrylic monomer or polyfunctional group polyurethane acroleic acid class monomer.
5. aqueous developable according to claim 1 or 2 exempts from chemical treatment temperature-sensitive version, it is characterised in that：Described cation
Initiator is salt compounded of iodine, one kind of sulfosalt or at least two；Cationic initiator heat decomposition temperature is 150-200 DEG C.
6. aqueous developable according to claim 5 exempts from chemical treatment temperature-sensitive version, it is characterised in that：Described infrared light radiation
It is cyanine dyes of the absworption peak in 750-850nm to absorb dyestuff.
7. aqueous developable according to claim 1 exempts from chemical treatment temperature-sensitive version, it is characterised in that：Described heat-sensitive layer coating
Dry weight is 8-15mg/dm2, described protective layer dry weight is 5-20mg/dm2。
8. aqueous developable as claimed in claim 1 exempts from the preparation method for being chemically treated temperature-sensitive version, it is characterised in that：It include with
Lower step：（1）Handle aluminum substrate support；(2) it is coated with heat-sensitive layer on aluminum substrate support after treatment；（3）In heat-sensitive layer
On coat protective layer.
9. aqueous developable according to claim 8 exempts from the preparation method for being chemically treated temperature-sensitive version, it is characterised in that：Described
Handling aluminum substrate support includes the sealing pores to the electrolyzing and coarsening of aluminum substrate support and anodic oxidation and progress, processing
Aluminum substrate support center line average boldness is 6 μm of 0. 4-0. afterwards.
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| CN108227384A (en) * | 2016-12-14 | 2018-06-29 | 乐凯华光印刷科技有限公司 | Negative type heat-sensitive CTP plate precursor with double-layer structure |
| CN109263338B (en) * | 2017-07-17 | 2021-09-14 | 乐凯华光印刷科技有限公司 | On-press development treatment-free thermosensitive plate and preparation method thereof |
| CN111103759B (en) * | 2018-10-26 | 2023-06-06 | 乐凯华光印刷科技有限公司 | Low-chemical-treatment thermosensitive plate and preparation method thereof |
| CN109839803A (en) * | 2019-01-25 | 2019-06-04 | 安徽强邦印刷材料有限公司 | A kind of heat susceptible coating for exempting from processing CTP editions suitable for water development |
| CN109835081A (en) * | 2019-01-25 | 2019-06-04 | 安徽强邦印刷材料有限公司 | A kind of double coating water developments exempt from processing CTP editions |
| JP7413394B2 (en) * | 2019-09-30 | 2024-01-15 | 富士フイルム株式会社 | On-press development type printing original plate, printing plate manufacturing method, and structure |
| CN113547857B (en) * | 2020-04-26 | 2023-04-07 | 浙江乾景新材料有限公司 | Multifunctional protective material composition for thermosensitive treatment-free lithographic printing plate and application thereof |
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Effective date of registration: 20180212 Address after: 473003 Nanyang Station Road, Henan, No. 718 Co-patentee after: Beijing Aerospace innovation patent investment center (limited partnership) Patentee after: Lucky Huaguang Graphics Co., Ltd. Address before: 473003 Nanyang Station Road, Henan, No. 718 Patentee before: Lucky Huaguang Graphics Co., Ltd. |