CN103879169B - A kind of positive-printing heat-sensitive CTP plate material of the ink of resistance to UV - Google Patents
A kind of positive-printing heat-sensitive CTP plate material of the ink of resistance to UV Download PDFInfo
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- CN103879169B CN103879169B CN201210563878.7A CN201210563878A CN103879169B CN 103879169 B CN103879169 B CN 103879169B CN 201210563878 A CN201210563878 A CN 201210563878A CN 103879169 B CN103879169 B CN 103879169B
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Abstract
The present invention has openly introduced a kind of thermal CTP plate material of the ink of resistance to UV, and it adopts high-quality aluminum plate foundation and two coating formula to manufacture and design. Comprise plate support, on support, be coated with the solvent resistance good resin bed of alkali solubility of holding concurrently, on resin bed, be coated with positive heat-sensitive photosensitive layer. It is to be formed by company's independent research that main film-forming resin in described resin bed also can be described as polymeric binder, and photosensitive layer is to be improved by the traditional individual layer thermosensitive CTP formula of company. It is high that this plate has speed, and site reduction is excellent, and plate-making operation tolerance is large, stable performance, the feature that printability is strong. Both can be specifically designed to UV ink printing, the long journey plate that prints that also can be used as conventional solvent ink printing uses, and better for above printing pressrun after baking.
Description
Technical field
The present invention relates to heat-sensitive positive-working lithographic plate, be specifically related to a kind of oil of resistance to UV that is applicable to CTPThe double-deck positive image thermosensitive lithographic printing plate of ink print.
Background technology
Along with the development of computer graphics disposal technology, people's notice has turned to inapplicable silver salt coated film, logicalCross laser beam or thermal head the directly photosensitive or thermal CTP system of imaging on base material of digital image-forming information. Use largeType semiconductor laser or YGA laser has following advantage than traditional photocuring method for platemaking: can expose by the short timeTo high-definition picture, reach the effect that saves time; Thermal CTP plate for system can operate under daylight, reaches provincePower effect.
In recent years, in long wave absorbing dye, add the technology of chemical amplifying type photoresist disclosed, for example JA-A-6-43633 discloses a kind of material, and it is by a kind of salt dyestuff, and acid-releasing agent and binding agent form. Expose by semiconductor laserThe similar techniques of coating plate-making is disclosed in JP-A-7-20629. This coating comprises IR dyes, the Bronsted acid of diving, alkaliProperty resin and a kind of phenolic resins. Use the JA-A-7-271029 of similar techniques to substitute potential quality above-mentioned by S-triazoleSon acid, but this conventional art is from angle the imperfection of use. One of the photosensitive version of this chemical amplifying type is seriousDefect is after exposure, to need a heat treated step, and due to different heating conditions, the quality stability of image is difficult to protectCard, and do not need the technology of heating steps to occur.
By infrared laser scan exposure, optical-thermal conversion material becomes heat energy that oleophylic coating is changed transform light energy,Dissolubility before and after coating exposure in alkaline-based developer changes, and from insoluble to dissolving, exposes the hydrophilic region of lower floor. SpeciallyProfit EP0823327 has described the positive-working lithographic printing plate of dissolution velocity generation significant change after this exposure, and it comprises polymerizationThing binding agent, IR absorbent and solubility inhibitor, it can make composition under IR radiation event, be insoluble to alkalescence unexposedDeveloper solution and be dissolved in alkaline-based developer under exposure status. Patent EP1072404 describes a kind of positive-type infra-red heat sensitive composition,Comprise polymeric binder and and solubility inhibitor, it can make heat-sensitive composition be insoluble to alkaline development in unexposed situationLiquid is dissolved in alkaline-based developer under exposure status, and wherein said solubility inhibitor is hydroxylated acrylate copolymer or is total toPolymers, is characterized in that part of hydroxyl is by carboxylic acid or its active substituent esterification. Patent WO19739894 has introduced in heat sensing layerIts exposed portion or unexposed portion have different deliquescent positive image thermosensitive lithographic printing plates in alkaline-based developer,Comprising: optical-thermal conversion material, the formula combination of alkali soluble resins and resistance solvent.
In CN1891455A, introduce and in lithographic plate heat-sensitive layer formula, added acrylamide and propylene sulphonylAmine improves the solvent resistance of lithographic plate, at CN1688657A (EP1554346B1), has introduced in lithographic plate temperature-sensitiveIn layer formula, add N-imide group to improve the solvent-resisting of lithographic plate, European patent EP 1506858 HesIn EP1738900, having introduced in lithographic plate heat-sensitive layer formula adds N-vinyl amide polymer to improve lithographic printingThe solvent-resisting of version has been introduced a kind of acid amides and imide structure unit of accessing on phenolic resins in WO2004035645Improve the solvent resistance of lithographic plate, but obviously galley solvent resistance is improved, but produces again new askingTopic, plate alkali resistance variation when the solvent resistance of plate increases, degradation under plate scratch resistance ability.
In patent US6040113, propose to adopt two coatings or overbrushing layered scheme to solve, on hydrophilic base surface at leastHave a water-repellent layer, it is infrared-sensitive top layer on it containing alkali soluble polymer, and underfill resin layer is phenolic resins, polyvinyl alcohol orContaining carboxylic acid polyalcohol resin. US Patent No. 6192799 and EP0950518B1 propose overbrushing layer positive heat-sensitive version and contain hydrophilic groupThe end,, dissolve in ground floor and the infrared-sensitive top layer that is insoluble to alkaline-based developer in alkaline developer, and at least one in two-layerLayer is containing surfactant, and underfill resin layer adopts NC Nitroncellulose class. Patent WO2009023103 proposes positive imageable material and containsOn the support of water-wetted surface, have in turn internal layer, contain main polymeric binder contain N-alkane methyl (alkyl) acrylamide orOne or more repetitives and acetals repetitive that alkoxyl-methyl (alkyl) acrylic acid is derivative. Two coating positive heat-sensitivesThe resin bed of CTP plate adopts different types of resin, has improved the performance of the anti-chemical reagent of plate, but has plate senseSpend low, plate develop difficulty and the low problem of plate development latitude.
Summary of the invention
The technical problem to be solved in the present invention is mainly poor for the anti-chemistry of current single coating positive heat-sensitive version, discomfortThe problems such as close UV ink printing, two coating positive heat-sensitive sensitivity are on the low side, and plate develops difficult, and tolerance is not high, propose a kind of endThe solvent resistance that layer the contains independent research applicable UV ink printing of the good copolymer of alkali solubility as main film-forming resin of holding concurrentlyDouble-deck positive image thermosensitive lithographic printing plate.
For solving the problems of the technologies described above, technical scheme of the present invention is as follows:
The positive-printing heat-sensitive CTP plate material of the ink of resistance to UV of the present invention, comprises plate support, is coated with alkali molten on supportProperty resin bed is coated with positive heat-sensitive photosensitive layer on alkali soluble resins layer; Described resin bed is by the solvent resistance alkali of holding concurrentlyThe film-forming resin that dissolubility is good and background dye and development chaotropic agent composition; The described solvent resistance good one-tenth of alkali solubility of holding concurrentlyFilm resin is the organic macromolecular copolymer of a kind of 3 yuan-5 yuan, is used for the monomer of copolymerization mainly to comprise two class groups, acidic-groupAnd polar group; Weight average molecular weight is between 15000-35000, and number-average molecular weight is between 7000-15000, at resin bedQuality percentage composition is more than 95%.
Being used for the acidic-group that the monomer of copolymerization comprises is R1-COOH，R2-OH，R3At least one in-Ph-OH, instituteThe polar group of stating is R4-NH2，R5-CN，R6-CO-NH2，R7-NH-CO-R8，R9-SO2-NH2In at least one, R wherein1-R9Be independently the alkyl containing 1-9 C, aryl, aralkyl separately.
Being used for acidic-group that the monomer of copolymerization comprises is preferably at least one in the monomer of following structural formula:
The described monomer with polar functional group is preferably at least one in the monomer shown in following structural formula:
The described solvent resistance good film-forming resin of alkali solubility of holding concurrently is used for the monomer of copolymerization and also comprises esters monomer, described inEsters monomer be at least one in the monomer shown in following structural formula:
Described development accelerant is any one in organic acid or acid anhydrides, the quality of development accelerant in resin bedPercentage composition is 5-10%.
Described background dye is in Victoria blue, alkaline bright blue, solvent blue, crystal violet, crystal violet or methylene blueOne or more, the quality percentage composition of background dye in resin bed is 1-3%.
Described resin bed is to be coated on support through 120 DEG C-135 after described component is fully dissolved in organic solventDEG C dry 2-3min form film, rete weight is 0.8-1.2g/m2。
The positive image thermosensitive lithographic printing plate of the ink of resistance to UV of the present invention has successively on the support of water-wetted surfaceResin bed and thermo-responsive photosphere, resin bed comprises copolymer adhesive, chaotropic agent, background dye; Thermo-responsive photosphere comprises film formingResin (being mainly phenolic resins), infrared absorbing agents, acid agent, resistance solvent and illuminating colour.
(1) lower-layer resin layer
In lower-layer resin layer, contain alkali solubility film-forming resin, chaotropic agent, illuminating colour.
1. the solvent resistance good film-forming resin of alkali solubility (copolymer adhesive) of holding concurrently
The screening that a Focal point and difficult point of the present invention is exactly lower floor's film-forming resin is with synthetic. Solve aforementioned said askingTopic, lower-layer resin layer must reach two technical indicators: the one, there is good anti-chemistry, the 2nd, there is good alkali moltenProperty. As a rule can be used to the synthetic resin of the monomer that comprises single kind group of imaging, alkali solubility and solvent resistance are difficult toTake into account simultaneously, such as linear phenolic resin, acrylic resin, polyvinyl alcohol, carboxylic acid polyalcohol resin etc. So the present invention proposesA kind of 3 yuan of-5 membered copolymers, are to have 3 to 5 to contain respectively polar group, and the monomer of acidic-group and ester class group altogetherPoly-forming. This by thering is the synthetic copolymer of different attribute monomer, optimize and revise Ke Yida by a certain proportion ofTo the alkali solubility all good performance indications of solvent resistance of holding concurrently.
The described monomer example that is used for synthetic copolymer adhesive has:
(1) there is the monomer of acidic functionality
(2) there is the monomer of polar functional group
(3) esters monomer
2. chaotropic agent
Chaotropic agent uses as a kind of development accelerant in resin bed, is mainly to add number acid in resin bedAcid anhydride or organic acid. For example: phthalic anhydride, tetrahydrophthalic anhydride, hexahydro phthalic anhydride, 3,4,5-tri-Methoxy cinnamic acid, p-methyl benzenesulfonic acid, DBSA, to toluenesulfinic acid, phosphenylic acid, benzoic acid, laurateWith ascorbic acid etc.
3. illuminating colour
In resin bed of the present invention, also comprise colouring agent, available background dye is a lot, general conventional PS version and temperature-sensitiveCTP version with background dye can, for example solvent blue, alkaline bright blue, Victoria's ethereal blue, phthalocyanine blue, malachite green, blackish green,Phthalocyanine green, crystal violet, crystal violet, ethyl violet, dimethyl yellow and fluorescein etc. In resin bed formula, can also comprise other interpolationsAgent is as binded reinforcing agent etc., resin bed coating weight 0.8-1.2g/m2。
(2) the thermo-responsive photosphere in upper strata
1. phenolic resins
The basic recipe of positive image thermosensitive lithographic printing plate heat-sensitive layer comprises absorbent, phenolic resins and resistance solvent. DoThat positive image thermosensitive lithographic printing plate has the infrared of data signal through semiconductor laser or YGA Laser emission by principleAfter the scanning of laser, unexposed part alkali soluble resin and infrared absorbing agents and resistance solvent associate, aobvious through alkaline-based developerMovie queen is not removed, and exposed portion changes into heat because infrared absorbing agents absorbs infrared light, has destroyed alkali soluble resin and infraredThe association that absorbent and resistance solvent occur, accelerates its dissolution velocity in alkaline-based developer, through alkaline development greatlyLiquid is removed after developing.
Phenolic resins comprises linear phenolic resin and polyethylene phenol resin, and linear phenolic resin can be by polycondensation reaction systemStandby, wherein one of monomer must be aromatic hydrocarbons, such as: phenol, orthoresol, metacresol, paracresol, 2,5-xylenol, 3,5-xylenol,Resorcinol, pyrogallol, bisphenols, bisphenol-A, triphenol, faces ethyl phenol, an ethyl phenol, to ethyl phenol, propyl phenoxy, normal-butylPhenol, tert-butyl phenol, 1-naphthols, beta naphthal. A minimum aldehyde or ketone. Wherein aldehyde can be formaldehyde, acetaldehyde, and valeral, benzaldehyde,Furfural. Ketone can be acetone, MEK, methyl n-butyl ketone, metaformaldehyde. Weight average molecular weight is determined by CPC. Arrive with 100015000 are advisable, and 1500 is best to 10000. Linear phenol-aldehyde resin mountain aldehyde and phenol condensation. Metacresol/paracresol/2 in phenol, 5-bis-Phenol/3,5-diphenol/phloroglucin/mixed proportion is 40-100/0-50/0-20/0-20/0-20. Or phenol/orthoresol/rightCresols/mixed proportion is 1-100/0-70/0-60. Polyethylene phenol resin can one or more hydroxy styrenes polymerization of mountain,Such as: adjacent this ethene of hydroxyl, a hydroxy styrenes, 4-Vinyl phenol, 2-(o-hydroxy-phenyl) propylene, 2-(hydroxy phenyl)Propylene, 2-(p-hydroxybenzene) propylene. Can be by substituting group on these hydroxy styrenes. Such as: chlorine, bromine, the halogen such as iodine and fluorine are formerSon, or C1-4Alkyl so that on corresponding resin with these groups. These polyethylene phenol resin are by one or more hydroxylStyrene polymerization. On it, can there is substituting group, on the aromatic ring of polyethylene phenol, be connected with C1-4Alkyl is better, and unsubstituted is better.
2. infrared absorbing agents
It is a kind of light absorbing dyestuff of absorption 650nm to 13OOnm wave band light that have. INFRARED ABSORPTION in the present inventionAgent also not exclusively absorbs ultraviolet light, or absorb but to not sensitization of ultraviolet light, so under the white light that contains Weak ultraviolet notImpact formula. In all infrared absorbing agents, preferably following IR dyes: cyanine dye, half cyanine dye, polymethin dyes,Squaraine dye (squariliumdye), crocic acid salt (crocniumdye), methine, fragrant methine, polymethine, pyransSalt dyestuff, thiapyran dyestuff, naphthoquinone dyestuff, anthraquinone dye, oxazole, thiazole, merocyanine, chain cyanine, koha, naphthalene cyanines,Phthalein is general, sulphur cyanines, and porphyrin, indoles three carbocyanines, dislike indoles three carbocyanines, and indoles is spoilt, triarylamine, polyaniline, polypyrrole, pyrroleAzoles quinoline azo, sulfo-pyrans sub-virtue, oxazines, polythiophene, oxidation indolizine, wherein cyanine dye, polymethin dyes, pyrans anchor saltDyestuff and thiapyran dyestuff are better. The polymethin dyes in these compounds with cyanine dye and structure arrives 900nm at 650nmWave band has absorption. There is pyrrole south salt dyestuff and thiapyran dyestuff and can absorb the light of 800nm to 1300nm wave band.
Preferred ingredient comprises the cyanine dyes of general formula (A):
Wherein each X can be S, O, NR or C (alkyl) independently2；
Each R1Can be alkyl, alkyl azochlorosulfonate or alkyl ammonium group independently;
R2Can be hydrogen, halogen, SR, S02R, OR or NR2；
Each R3Can be hydrogen, alkyl, COOR, OR, SR, S0 independently3 -、NR2, halogen and not necessarily replace benzo thickRing;
A-Represent anion;
---represent nonessential five yuan or six-membered carbon ring;
Wherein each R can be hydrogen, alkyl and aryl independently;
Wherein each n can be 0,1,2 or 3 independently.
If R1Alkyl azochlorosulfonate, owing to having formed inner salt, so A-Can not exist, and alkali metal cation conductCounter ion will be essential. If R1Be alkyl ammonium group, will need the second anion as counter ion. The second anion canWith with A-Identical can be maybe different anion.
The photosensitive composition infrared Absorption dyestuff that is suitable for heat-sensitive positive-working CTP in the present invention is to contain as mentioned above sunThe cyanine dye of ion and anion salt structure, the mass ratio in plate coating is 3-20%, is preferably 5-10%.
3. acid agent
After infrared laser scanning, the infrared absorbing agents in heat-sensitive layer and resin bed absorbs heat, the product of exposure areaAcid agent occurs to decompose produces acid, and the solubility property in alkaline-based developer is strengthened, and contains IR dyes acid agent in resin bed simultaneously,The heat that IR dyes absorbs is easy to conduction and causes acid agent generation acid-producing, and unexposed part and IR dyes occurCertain effect of concluding, the dissolubility in alkaline-based developer weakens, improved like this plate sensitivity, accelerated the speed of developingDegree, has improved development latitude.
Acid agent comprises all sour materials that produce after irradiation, mainly comprises drone salt, organohalogen compounds, sulfonic acidEster, triazines and sulfohydrazide hydrazone class.
Drone salt acid agent comprises iodine drone salt, diazol and sulfonate, and example has:
In drone salt acid agent, also comprise the acid agent combining with the structure of IR dyes, there is heat and produce sour workWith. Structure is as follows:
Y is the alkyl sulfonic acid base of hydrogen, halogen, alkane, diphenylamines, phenyl sulphur, a 1-4 C atom. R1, R2, R3, R4 be respectively H,Sulfonic acid. Z1, Z2 are phenyl or naphthyls. Z3 is hydrogen atom, cyclohexyl or cyclopenta. X1, X2 are respectively S, O, NH, CH2, CMe2。QIt is father-in-law's cation. N is 1-4, and m is 1-3.
Organohalogen compounds acid agent example has:
Sulphonic acid ester acid agent example has:
Triazines acid agent example has:
Sulfohydrazide hydrazone class acid agent example has:
To tert-butyl benzene sulfohydrazide cyclohexanone hydrazone
2-naphthalene sulfonyl hydrazine cyclohexanone hydrazone
Above acid agent use capable of being combined if necessary, the present invention is drone salt acid agent preferably.
4. the molten chaotropic agent of resistance
If resistance solvent can reduce and add the resistance solvent effect can be better in the dissolubility formula of unexposed portion. Resistance solventEffect reason in formula it be unclear that. But there is any to affirm, be added with the component of resistance solvent at exposed portion notWork and effective at last exposed portion. And can find out in the contrast of exposed portion and last exposed portion that resistance solvent has and addStrong insoluble characteristic. So more be conducive to form good image. The addition of resistance solvent is preferably imaging layer alkali soluble resin weightThe 2-10% of amount.
A lot of compounds can be used as resistance solvent, but it should be able to keep photosensitive coating under certain stable condition, and it is in room temperatureUnder should be solid, or fusing point is the liquid of 180 degree. This compounds can be sulphonic acid ester, phosphate, aromatic esters, fragranceFamily's sulphonic acid ester, fragrant two sulfones, carboxylic acid anhydrides, aromatic ketone, aromatic aldehyde, aromatic amine, aromatic ester, these compounds can separately or mixClose rear use.
Sulfonic acid esters is such as ethyl benzenesulfonat, the just own ester of benzene sulfonic acid, benzene sulfonic acid phenyl ester, benzene sulfonic acid benzyl ester, benzene sulfonic acid benzeneEthyl ester, ethyl p-toluenesulfonate, the p-methyl benzenesulfonic acid tert-butyl ester, p-methyl benzenesulfonic acid n-octyl, p-methyl benzenesulfonic acid phenyl ester, to toluene sulphurAcid phenethyl ester, 1-naphthalene sulfonic aicd ethyl ester, 2-naphthalene sulfonic acids phenyl ester, 1-naphthalene sulfonic aicd phenyl ester 1-naphthalene sulfonic aicd phenethyl ester: diphenyl sulphone (DPS) or diformazanSulfone.
Phosphoric acid ester: trimethyl phosphate, triethyl phosphate, tricresyl phosphate (2-ethyl) pentyl ester, triphenyl phosphate, tricresyl phosphate(2-aminomethyl phenyl) ester, tricresyl phosphate methylol phenyl ester, tricresyl phosphate (1-naphthalene) ester, aromatic carboxylates's class: methyl benzoate, benzoic acidN-pentyl ester, phenol benzoate, benzoic acid 1-tea ester, benzoic acid n-octyl or three (positive butoxy carbonyl) s-triazole.
Carboxyanhydrides: single two Trichloroacetic anhydrides, phenylsuccinic acid acid anhydride, apple acid anhydrides, adjacent benzene two dicarboxylic acid anhydrides, benzoic acidAcid anhydride. Fragrance ketone: benzophenone, acetophenone, even benzene and 4,4 ,-2 methylamino benzophenone. Aldehydes: to dimethylamino benzaldehyde,P-methoxybenzal-dehyde, 4-chloro-benzaldehyde and 1-naphthaldehyde, aromatic amine is as triphenylamine, diphenylamines, trihydroxy phenyl amine, hexicholBase naphthylamine. Aromatic ether is as ethylene glycol bisthioglycolate diphenyl ether, 2-methoxynaphthalene yl diphenyl ether. 4,4 ,-2 ethyoxyl two phenolic ethers.
Some structures that these compounds have can be connected on resin them. As: sulphonic acid ester can pass through esterKey or hydroxyl and linear phenolic resin or polyethylene phenol resin link together.
Scold aqueous polymer to represent the applicable resistance solvent of another type, this base polymer be it seems by repelling from coating wettingAgent and improve the developer tolerance of coating, scolds aqueous polymer can add in the glue-line that comprises hydrophobic polymer, also can doFor the individual course on the glue-line of hydrophobic polymer, also can become barrier layer, heat sensing layer and developer solution shielding are come, andBarrier layer can dissolve in developer solution, for example, comprise the polymer of the construction unit of siloxanes and/or perfluoroalkyl, comprises benzeneMethyl siloxane and/or dimethyl siloxane and oxirane and/or epoxy propane copolymer.
(3) lithographic plate plate is manufactured
Above-mentioned heat sensing layer formula through coating process be applied to there is hydrophilic table and support on.
Coating process: slope streaming extrusion coated, rotary coating, soaks coating, anilox roll coating, the coating of air scissors,Print roll coating, scrapes version coating, curtain coating etc.
Coating squence Shi Xiantu lower floor, is coated with then heated-air drying of upper strata after being dried again. When coating, it should be noted that upper and lowerThe control of two layers of coatings thickness and baking temperature: resin bed is to be coated in aluminium plate support after fully being dissolved by organic solvent to pass through120 DEG C-135 DEG C, 2-3min is dried film forming, and weight is 0.8-1.2g/m2. After thermo-responsive photosphere is fully dissolved by organic solventAt 120 DEG C of-135 DEG C of temperature, dry 2-3min and be coated on the resin bed after drying and forming-film, weight is 0.5-0.9g/m2。
This coating may further include one or more different layers, and except following examples coating, this coating canComprise glue-line, to improve the cohesive of coating to base material, cover layer, protective finish is exempted from and is polluted or mechanical damage, and photo-thermal transformsLayer, it comprises infrared absorbing agents.
Support: version base can sufficient aluminium, zinc, steel or copper, or contain chromium, zinc, iron, the metallograph of aluminium. In this formula, useAluminium plate is best. Aluminium plate surface is carried out known method and is processed and obtain water-wetted surface.
(4) offscreen version manufacture method of printing
(1) imaging exposure process
The imaging exposure of positive heat-sensitive ox lithographic printing plate plate can be passed through infrared or near-infrared laser and bombardment with laser beamsExposure, wave-length coverage again 800-1200nm positive image thermosensitive lithographic printing plate absorbs the light of this wave-length coverage, this exposureLight source is modal exposure method, this exposure method be easy to by emission wavelength again the laser of 830nm and 1064nm comeRealize. The effective exposure being applicable to realizes by imaging platemaking machine, as: CreoTrendsettcr (CREOCorp.BritishC0lumhia, Canada) and GerberCrescent42T (production of Gerber company).
The imaging exposure of positive image thermosensitive lithographic printing plate can be used one equipment easily, comprises a temperature-sensitive and printsBrush, imaging device is applicable at least connecting a thermal print head, is generally all a branch of thermal print head, as TDKNo.LV5416 is as in hot facsimile machine and heat sublimation printing machine. When by thermal head imaging exposure, positive thermal-sensitive offsetVersion plate must can absorb infra-red radiation.
In addition, imaging signal is during as computer storage data, and this file will just can be accepted by RIP program, as RIPThe page number descriptive language that can accept input, this language will have more data file.
(2) developing process
The developer of positive image thermosensitive lithographic printing plate can be any liquid or solution, and it can permeate and dissolve senseThe exposure area of photosphere, and unexposed region can not be permeated and dissolve. The developer solution of tradition lithographic printing plate plate is all to useSig water by plate is carried out to development treatment, just leaves the slight projection of the oleophylic that has no the formation of light sensation photosphere on the space of a whole pageCamegraph. Can the photosensitive layer of non-image part, remove from the space of a whole page after development completely, depends on molten to diluted alkaline of photosensitive layerXie Xing. Conventional temperature-sensitive plate developing liquid is alkaline solution at present, is mainly made up of developer, protective agent, wetting agent and solvent etc.Developer is for dissolving the photosensitive layer that positive picture CTP plate has exposed. Conventional strong alkaline substance, as NaOH, potassium hydroxide, silicic acidSodium, potassium silicate etc. Protective agent also claims inhibitor, can stablize developer solution performance, can reduce developer little right at developing process simultaneouslyThe etch of version base, also can protect the photosensitive layer at picture and text position not to be subject to soaking of developer solution molten. The effect of wetting agent is to reduce developer solutionSurface tension, make developer solution can soak quickly and evenly the space of a whole page, be beneficial to develop uniformity. Conventional wetting agent has tenThe agriculture surface-active agents such as dialkyl benzene sulfonic acids sodium, tween, are all glutinous thick liquids, and these two kinds of surfactants are except having wetabilityAlso have the performance of emulsion dispersion, thereby in developing process, forme is also helped to the function of washing outward. Developer solution is taking water as solvent,The general deionized water that adopts.
Lithographic plate manufacture method may further include the process of protection glue
The invention has the beneficial effects as follows: the positive image thermosensitive lithographic printing plate that contains said structure and component has high senseDegree, high development latitude, high pressrun, good net-point quality and good solvent resistance.
Detailed description of the invention
Embodiment 1-6
The hold concurrently synthetic method of the good film-forming resin of alkali solubility of solvent resistance in the present invention is as follows:
The synthetic of following copolymer is all synthetic by the method for homopolymers, is all to have stirring, in the container of condenser pipe(preferably pass into nitrogen, get rid of oxygen in bottle), adds the solvent for dissolved monomer, is generally DMF, soAfter the monomer of be used for copolymerization is added to sub-fraction in proportion, and (initator is azo or has to add appropriate initatorOne in machine peroxide), stirring and dissolving 10-20 minute. Be dissolved to solution near-transparent, begin to warm to 70-80 DEG C, reactionAfter one hour, remaining part drips with funnel, and be preferably in one hour and drip off, then successive reaction 4-5 hour, be down to room temperature,Add 0.5g hydroquinones (being dissolved in 50ml ethyl cellosolve), stir 10 minute hands, then reaction mixture is slowly added to 4 litersIn water, obtain white solid, filter, clean three times, be placed in vacuum drying chamber inner drying.
Synthesizing of copolymer adhesive resin 01
In 1000ml four-hole boiling flask, load onto stirring, condenser pipe, dropping funel pass into nitrogen and get rid of oxygen in bottle, addEnter ethyl cellosolve 200mlDMF200ml, dibenzoyl peroxide 0.6g, acrylamide 20g, starts stirring and dissolving, adds firstBase acrylic acid 5g, acrylonitrile 5g, N-phenylmaleimide 10g, stir 10 minutes, begin to warm to 75 DEG C, react 1 hour,Start to drip mix monomer (acrylamide 15g, methyl methacrylate 5g dissolve in 50ml ethyl cellosolve), in 1 hourDrip off, continue reaction 4 hours, after reaction finishes, be down to room temperature, add 0.5g hydroquinones (to be dissolved in 50ml ethyl cellosolveIn), stir 10 minute hands, then reaction mixture is slowly added in 4 premium on currency, obtain white solid, filter, clean three times, putIn vacuum drying chamber inner drying.
All the other 02-07 polymer monomers structures and ratio are in table 1.
Table 1
Prepare the resin bed 1-7 of positive image thermosensitive lithographic printing plate by following formula:
Prepare the heat-sensitive layer 1-7 of positive image thermosensitive lithographic printing plate by following formula:
The thermo-responsive photosphere in above embodiment upper strata is constant, and lower-layer resin strata compound is followed successively by the synthetic 1-7 of table one.
Comparative example 1
Traditional individual layer thermal formulations
Comparative example 2
Upper strata is constant by 01 example, and the good phenolic resins of anti-alcohol that lower-layer resin layer is modification is made main film-forming resinFormula
Lower-layer resin layer formula is as follows:
Comparative example 3
Lower floor is constant by resin bed 02 example, the formula of individual layer positive heat-sensitive dicyandiamide solution for upper strata
Upper thermosensitive layer formula is as follows:
The physical property of resin bed and heat-sensitive layer coating fluid is as shown in table 2 and table 3.
The physical property of table 2 resin bed coating fluid
The physical property of table 3 heat-sensitive layer coating fluid
The manufacture of positive image thermosensitive lithographic printing plate in above-described embodiment
The preferred aluminum substrate of version base, obtains water-wetted surface through following processing.
(1) decontamination
Aluminium plate carries out decontamination processing, and with organic solvent, acid or buck cleaning surface, meltage is at 5-8g/m2。
(2) electrolysis
Require the lipophile of plate picture and text part good, blank parts hydrophily will be got well, and blank parts hydrophilicity needs wellBy aluminium plate is carried out to sand screen mesh, make blank sand holes part water storage and oleophylic not, the formation electrolysis of Grains, with aluminium plate andGraphite is as two electrodes, in the hydrochloric acid solution of electrolyte: 6-20g/L, and 50HZ alternating current, electric current 20-100A/dm2, liquid temperature30-60 DEG C, electrolysis time 5-90 second, controls Ra=0.5-0.6um.
(3) oxidation
In order to improve mechanical strength, the enhancing wearability on aluminium plate surface and to improve hydrophily and will carry out anode to aluminium plate surfaceOxidation processes, defends with the sulfuric acid solution of 15%-30%, at 20-60 temperature, and 5-250 electrolytic treatments second, aluminium ion concentration: 0.5-5g/L, uses direct current, electric current 1-15A/dm2. control oxide-film=2-3g/m2。
(4) sealing of hole
Aluminium plate agriculture face micropore after electrolysis and anodic oxidation is a lot, and the object of sealing of hole is blocked these micropores exactly, usesSodium silicate aqueous solution soaks the object that realizes hydrophiling and sealing of hole.
(5) coating
Adopt slope streaming extrusion coated, lower floor's coating weight is with 0.8-1.2g/m2Be advisable, upper strata coating weight is with 0.6-0.8g/m2。
(6) dry
Adopt heated-air drying, temperature is 20-150 DEG C of degree, is advisable with 100-130 DEG C.
(7) balance
The plate of producing need to be placed 7 days in room temperature, carries out detecting after balance.
The method for testing performance of positive heat-sensitive planographic plate and experimental result
Above-mentioned positive heat-sensitive planographic plate material obtains lithographic plate through steps of processing.
(1) with heat shock light beam, above-mentioned positive heat-sensitive planographic plate material imaging is exposed.
(2) with alkaline-based developer, the positive heat-sensitive planographic plate material of above-mentioned imaging exposure is developed.
1, relative sensitivity detection method
In SCREEN8600E platemaking machine, with carrying test-strips, imaging screening 175lpi, output resolution 2400dpi,According to following conditions of exposure (in table 3) and development conditions (in table 4), on sample, carry out the scanning plate-making of different laser energy,Then by the definite optimum exposure amount of laser light of following methods, be its best sensitivity relatively, its value is larger, and plate sensitivity is lower.
A) first the menu of Ai Seli 528 type Density Measuring Instruments is adjusted under site test catalogue
B) also measure blank density value with Ai Seli 528 type Density Measuring Instruments
C) measure field density value with the secret Density Measuring Instrument of Ai Seli 528 type again
D) finally measure 50% plain net value under different exposure energies, until find out in step-wedge bar 50% plain net region be50% show value, this value is the relative sensitivity of plate.
E) record the relative sensitivity of plate.
F) test-strips below has a row site thin out to nothing gradually along with sensitivity value increases, and this row site disappears from having to nothingThe corresponding sensitivity of critical point of losing is the sensitivity of 1: 1 of plate, also can be described as plate normal sensibility.
G) by different sensitivity plate blank spaces in test-strips after acetone titration exposure, until blank space titration and not titration groundSide can't see any obvious circle trace, is clean point.
Testing result is in Table
Table 4 conditions of exposure
Table 5 development conditions
| Developer solution model | TPD-3 developer solution |
| Developing machine | PCX-85 (India) developing machine |
| Development temperature | 23℃ |
| Developing powder | 30 seconds (1lOcm/min): |
| Developer solution, electrical conductivity is controlled at | 89-91ms/Cm |
| Dynamically supplementing of developer solution | 120ml/m2 |
Table 6 is sensitivity testing result relatively
2, the detection of development latitude
In SCREEN8600E platemaking machine, carry out according to the light exposure of 1.3 times of the value of optimum exposure obtained aboveExposure, has just carried test-strips and on sample, has carried out the scanning plate-making of different laser energy, different showing under 23 DEG C of development temperaturesThe shadow time, under (selecting 10s, 20s, 30s, 40s here) condition, example edition is developed to process and process, can make plate reachThe developing time of instructions for use (blank space is not kept on file, density OD value < 0.29, coating does not subtract film on the spot, site reduction 3-99%)Peak and the difference of minimum be the development latitude of this plate, experimental result is as table 7:
Table 7
3, the alkali resistant of coating and solvent resistance detect
The plate of coating after dry coating is cut into the square of 10 × 10cm, 4 squares of each sample, do respectively asLower coating performance detects:
1. weigh coating weight
First on the electronic balance that is accurate to 0.0001, weigh up the weight W of each belt transect coating square1, with mixed solvent orAcetone washes away coating, then the W that weighs after drying2。W1-W2Be the weight of coating.
Coating alkali resistant loss in 2.30 seconds
On the electronic balance that is accurate to 0.0001, weigh up the weight W of each belt transect coating square1, then ready aobviousIn shadow liquid, temperature is generally 25 DEG C of immersions 30 seconds, takes out and dries rear weigh W2，W1-W2/W1Be alkali resistant loss in 30 seconds.
Coating alkali resistant loss in 3.60 seconds
On the electronic balance that is accurate to 0.0001, weigh up the weight W of each belt transect coating square1, then ready aobviousIn shadow liquid, (TPD-3) temperature is generally 25 DEG C of immersions 60 seconds, takes out and dries rear weigh W2，W1-W2/W1Be 60 seconds and resistAlkali loss.
4.60 second solvent loss
On the electronic balance that is accurate to 0.0001, weigh up the weight W of each belt transect coating square1, then ready molten(EC of 60% weight portion, the IPA of 40% weight portion) is inner in agent, and temperature is generally 25 DEG C and soaks 60 seconds, takes out and dries rear weighingWeight W2，W1-W2/W1Be solvent loss in 60 seconds.
Table 8 coating performance testing result
4, the detection of pressrun
Make with site, on the spot, the wear-resisting test-strips of picture and text, put into have rubber ball, diamond dust, graining liquid (millVersion liquid can be according to actual print situation oneself preparation, generally form and fountain solution similar) drum type device in grind 30-60 and divideClock, then takes out wear rib, observes the picture and text damaed cordition on it, can simply judge the pressrun of plate. Following table 9 is grainingThe abrasion condition of 30 DEG C of mills of liquid plate picture and text after 30 minutes.
Table 9
| Embodiment | Picture and text situation before graining | Picture and text situation after graining |
| Embodiment 1 | Site 2-99% on the spot 1.36 | Site 5-90% on the spot 0.86 |
| Embodiment 2 | Site 2-99% on the spot 1.37 | Site 5-90% on the spot 0.89 18 --> |
| Embodiment 3 | Site 2-99% on the spot 1.36 | Site 5-90% on the spot 0.96 |
| Embodiment 4 | Site 2-99% on the spot 1.38 | Site 5-85% on the spot 0.86 |
| Embodiment 5 | Site 2-99% on the spot 1.35 | Site 5-90% on the spot 0.93 |
| Embodiment 6 | Site 2-99% on the spot 1.34 | Site 5-90% on the spot 1.02 |
| Embodiment 7 | Site 2-99% on the spot 1.33 | Site 5-90% on the spot 1.01 |
| Comparative example 1 | Site 2-99% on the spot 1.36 | Fall light |
| Comparative example 2 | Site 2-99% on the spot 1.38 | Site 5-80% on the spot 0.57 |
| Comparative example 3 | Site 2-99% on the spot 1.16 | Substantially fall light 0.35 on the spot |
Can fully prove conclusion of the present invention by above test.
Claims (10)
1. a positive-printing heat-sensitive CTP plate material for the ink of resistance to UV, comprises plate support, is coated with alkali soluble resins on supportLayer is coated with positive heat-sensitive photosensitive layer on alkali soluble resins layer; It is characterized in that: described resin bed is by solvent resistanceThe good film-forming resin of alkali solubility and the background dye held concurrently and development accelerant composition; Described film-forming resin is a kind of 3 yuan-5The organic macromolecular copolymer of unit, is used for the monomer of copolymerization and mainly comprises two class groups: acidic-group and polar group; Weight average dividesSub-weight range is between 15000-35000, and number-average molecular weight is between 7000-15000; The monomer that contains polar group accounts for wholeThe quality percentage composition of individual synthon is 45-65%, and the quality percentage that the monomer that contains acidic-group accounts for whole synthon containsAmount is 5-25%; This film-forming resin is more than 95% at the quality percentage composition of resin bed.
2. the positive-printing heat-sensitive CTP plate material of the ink of resistance to UV according to claim 1, is characterized in that: be used for the monomer institute of copolymerizationThe acidic-group comprising is R1-COOH，R2-OH，R3At least one in-Ph-OH; Described polar group is R4-NH2，R5-CN，R6-CO-NH2，R7-NH-CO-R8，R9At least one in-SO2-NH2; R wherein1-R9Separately independently for containing 1-9The alkyl of individual C, aryl, aralkyl.
3. the positive-printing heat-sensitive CTP plate material of the ink of resistance to UV according to claim 1, is characterized in that: be used for the monomer of copolymerizationThe monomer of the acidic-group comprising is at least one in the monomer of following structural formula:；
Being used for the monomer of the polar group that the monomer of copolymerization comprises is at least one in the monomer shown in following structural formula:。
4. the positive-printing heat-sensitive CTP plate material of the ink of resistance to UV according to claim 1, is characterized in that: described solvent resistance is held concurrentlyThe film-forming resin that alkali solubility is good is used for the monomer of copolymerization and also comprises esters monomer, and described esters monomer is following structural formula instituteAt least one in the monomer showing:
。
5. the positive-printing heat-sensitive CTP plate material of the ink of resistance to UV according to claim 1, is characterized in that: described development accelerantFor any one in organic acid or acid anhydrides; The quality percentage composition of development accelerant in resin bed is 5-10%.
6. the positive-printing heat-sensitive CTP plate material of the ink of resistance to UV according to claim 1, is characterized in that: described background dye isVictoria blue, alkaline bright blue, solvent blue, crystal violet, at least one in crystal violet and methylene blue, background dye is at resinQuality percentage composition in layer is 1-3%.
7. the positive-printing heat-sensitive CTP plate material of the ink of resistance to UV according to claim 1, is characterized in that: described in described resin bed isSolvent resistance is held concurrently after the good film-forming resin of alkali solubility, background dye and development accelerant fully dissolve in organic solvent and is coated withOverlay on support and dry through 120 DEG C-135 DEG C the film that 2-3min forms, rete weight is 0.8-1.2g/ ㎡.
8. the positive-printing heat-sensitive CTP plate material of the ink of resistance to UV according to claim 1, is characterized in that: described plate supportFor the processing of process electrochemistry graining, tegmen oxidation processes, the aluminum plate foundation of sealing of hole processing.
9. the positive-printing heat-sensitive CTP plate material of the ink of resistance to UV according to claim 1, is characterized in that: described positive heat-sensitive sensitizationLayer comprises: film-forming resin, and IR dyes, thermic produces acid source, hinders molten dissolution compound, illuminating colour; Described film-forming resinFor linear phenolic resin, weight average molecular weight is 5000-20000, Mw/MnFor 1.5-2.0, the quality of film-forming resin in photosensitive layerPercentage composition is 40-80%.
10. the positive-printing heat-sensitive CTP plate material of the ink of resistance to UV according to claim 9, is characterized in that: described thermic produces acid sourceFor drone salt, organohalogen compounds, sulphonic acid ester, triazines and sulfohydrazide hydrazone class are produced at least one in acid source; Described resistance is molten shortDissolving compound is sulphonic acid ester, at least one in carboxylic acid ester compound; Described positive heat-sensitive photosensitive layer is described film forming treeFat, IR dyes, thermic produces acid source, hinders after molten dissolution compound and illuminating colour fully dissolve in organic solvent and is coated in treeOn fat layer, through 120 DEG C-135 DEG C, 2-3min is dried the film forming, and weight is 0.5-0.9g/ ㎡.
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| CN106364209B (en) * | 2016-11-04 | 2018-11-09 | 中国科学院理化技术研究所 | Thermosensitive treatment-free lithographic printing plate material containing thermosensitive protective layer and application |
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| CN109774334B (en) * | 2017-11-11 | 2021-11-30 | 乐凯华光印刷科技有限公司 | Positive thermosensitive UV-resistant ink CTP plate |
| CN108333878A (en) * | 2018-01-25 | 2018-07-27 | 上海宝士嘉印刷器材有限公司 | The single layer ink of resistance to UV heat-sensitive CTP plate is imaged coating |
| EP3845394A4 (en) * | 2018-08-31 | 2021-10-27 | FUJIFILM Corporation | Planographic printing original plate, method for producing planographic printing plate, planographic printing method and curable composition |
| WO2020080067A1 (en) * | 2018-10-17 | 2020-04-23 | 富士フイルム株式会社 | Planographic printing plate precursor, and production method for planographic printing plate |
| CN113795533B (en) * | 2019-01-31 | 2024-09-13 | 索尼集团公司 | Hologram recording composition, hologram recording medium, optical element, device and component, and method of forming hologram diffraction grating |
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