CN103879169A - Positive image thermo-sensitive CTP printing plate material capable of resisting UV printing ink - Google Patents
Positive image thermo-sensitive CTP printing plate material capable of resisting UV printing ink Download PDFInfo
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- CN103879169A CN103879169A CN201210563878.7A CN201210563878A CN103879169A CN 103879169 A CN103879169 A CN 103879169A CN 201210563878 A CN201210563878 A CN 201210563878A CN 103879169 A CN103879169 A CN 103879169A
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Abstract
The invention discloses positive image thermo-sensitive CTP printing plate material capable of resisting UV printing ink. The positive image thermo-sensitive CTP printing plate material made by high-quality aluminum plate base and double coatings comprises a plate material support body. A resin layer good in solvent resistance and alkaline solubility coats the support body. A positive image thermo-sensitive photosensitive layer coats the resin layer. The main film forming resin also called polymer binder in the resin layer is independently researched and developed by the inventor company, and the photosensitive layer is modified by traditional single-layer thermo-sensitive CTP of the inventor company. The plate material is high in photosensitivity, excellent in screen dot reduction, large in plate making operation tolerance, stable in performance and high in printing adaptability. The plate material can be specially used for UV ink printing and also be used as the long-printing-process plate material of traditional solvent ink printing, and better printing durability is achieved when the plate material is applicable to the mentioned printing after baking.
Description
Technical field
The present invention relates to heat-sensitive positive-working lithographic plate, be specifically related to a kind of double-deck positive image thermosensitive lithographic printing plate of the ink printing of resistance to UV that is applicable to CTP.
Background technology
Along with the development of computer graphics disposal technology, people's notice has turned to inapplicable silver salt coated film, by laser beam or thermal head the directly photosensitive or thermal CTP system of imaging on base material of digital image-forming information.Use large-scale semiconductor laser or YGA laser to there is following advantage than traditional photocuring method for platemaking: can expose and obtain high-definition picture by the short time, reach the effect that saves time; Thermal CTP plate for system can operate under daylight, reaches labor-saving effect.
In recent years, add the technology of chemical amplifying type photoresist disclosed in long wave absorbing dye, 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.Disclosed in JP-A-7-20629 by the expose similar techniques of coating plate-making of semiconductor laser.This coating comprises IR dyes, dive Bronsted acid, basic resin and a kind of phenolic resins.Use the JA-A-7-271029 of similar techniques to substitute latent Bronsted acid above-mentioned by S-triazole, but this conventional art is from angle the imperfection of use.A major defect of the photosensitive version of this chemical amplifying type is after exposure, to need a heat treated step, and due to different heating conditions, the quality stability of image is difficult to guarantee, and does 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, and the dissolubility before and after coating exposure in alkaline-based developer changes, and from insoluble to dissolving, exposes the hydrophilic region of lower floor.Patent EP0823327 has described the positive-working lithographic printing plate of dissolution velocity generation significant change after this exposure, it comprises polymeric binder, IR absorbent and solubility inhibitor, it can make composition under IR radiation event, be insoluble to alkaline-based developer and be dissolved in alkaline-based developer under exposure status unexposed.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-based developer in unexposed situation, under exposure status, be dissolved in alkaline-based developer, wherein said solubility inhibitor is hydroxylated acrylate copolymer or copolymer, it is characterized in that part of hydroxyl is by carboxylic acid or its active substituent esterification.Patent WO19739894 has introduced in heat sensing layer its exposed portion or unexposed portion has 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 sulfonamide to improve the solvent resistance of lithographic plate, at CN1688657A (EP1554346B1), having introduced in lithographic plate heat-sensitive layer formula adds N-imide group to improve the solvent-resisting of lithographic plate, in European patent EP 1506858 and EP1738900, having introduced in lithographic plate heat-sensitive layer formula adds N-vinyl amide polymer to improve the solvent-resisting of lithographic plate, in WO2004035645, introduce a kind of solvent resistance that accesses acid amides and imide structure unit and improve lithographic plate on phenolic resins, but, obviously galley solvent resistance is improved, but produce again new problem, 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, have a water-repellent layer at least, it,, containing alkali soluble polymer, is infrared-sensitive top layer on it, underfill resin layer is phenolic resins, polyvinyl alcohol or containing carboxylic acid polyalcohol resin.At the bottom of US Patent No. 6192799 and EP0950518B1 proposition overbrushing layer positive heat-sensitive version contain hydrophilic group, dissolve in ground floor and the infrared-sensitive top layer that is insoluble to alkaline-based developer in alkaline developer, and in two-layer, at least one deck is containing surfactant, and underfill resin layer adopts NC Nitroncellulose class.On the support that patent WO2009023103 proposition positive imageable material contains water-wetted surface, there is in turn internal layer, contain main polymeric binder and contain N-alkane methyl (alkyl) acrylamide or derivative one or more repetitives and the acetals repetitive of alkoxyl-methyl (alkyl) acrylic acid.The resin bed of two coating positive-printing heat-sensitive CTP plate materials adopts different types of resin, has improved the performance of the anti-chemical reagent of plate, but exists plate sensitivity low, plate development 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, be not suitable for UV ink printing, two coating positive heat-sensitive sensitivity are on the low side, plate develops difficult, the problems such as tolerance is not high, propose solvent resistance that a kind of bottom the contains independent research double-deck positive image thermosensitive lithographic printing plate of the good copolymer of alkali solubility as the applicable UV ink printing of main film-forming resin of holding concurrently.
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 soluble resins layer on support, is coated with positive heat-sensitive photosensitive layer on alkali soluble resins layer; Described resin bed is made up of the hold concurrently good film-forming resin of alkali solubility and background dye and development chaotropic agent of solvent resistance; The described solvent resistance good film-forming resin of alkali solubility of holding concurrently 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-group and polar group; Weight average molecular weight is between 15000-35000, and number-average molecular weight, between 7000-15000, is more than 95% at the quality percentage composition of resin bed.
Being used for the acidic-group that the monomer of copolymerization comprises is R
1-COOH, R
2-OH, R
3at least one in-Ph-OH, described polar group is R
4-NH
2, R
5-CN, R
6-CO-NH
2, R
7-NH-CO-R
8, R
9-SO
2-NH
2in at least one, R wherein
1-R
9be 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, and described esters monomer is at least one in the monomer shown in following structural formula:
Described development accelerant is any one in organic acid or acid anhydrides, and the quality percentage composition of development accelerant in resin bed is 5-10%.
Described background dye is one or more in Victoria blue, alkaline bright blue, solvent blue, crystal violet, crystal violet or methylene blue, and the quality percentage composition of background dye in resin bed is 1-3%.
Described resin bed is to be coated on support and to dry through 120 DEG C-135 DEG C the film that 2-3min forms after described component is fully dissolved in organic solvent, and rete weight is 0.8-1.2g/m
2.
The positive image thermosensitive lithographic printing plate of the ink of resistance to UV of the present invention has successively resin bed and thermo-responsive photosphere on the support of water-wetted surface, and resin bed comprises copolymer adhesive, chaotropic agent, background dye; Thermo-responsive photosphere comprises film-forming resin (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 problem, lower-layer resin layer must reach two technical indicators: the one, there is good anti-chemistry, and the 2nd, there is good alkali solubility.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 to take into account simultaneously, such as linear phenolic resin, acrylic resin, polyvinyl alcohol, carboxylic acid polyalcohol resin etc.So the present invention proposes a kind of 3 yuan of-5 membered copolymers, is to have 3 to 5 to contain respectively polar group, the monomer copolymerization of acidic-group and ester class group forms.Thisly optimize and revise by a certain proportion of by thering is the synthetic copolymer of different attribute monomer, can reach 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 in resin bed, to add some acid anhydrides or organic acid.For example: phthalic anhydride, tetrahydrophthalic anhydride, hexahydro phthalic anhydride, 3,4,5-trimethoxy cinnamic acid, p-methyl benzenesulfonic acid, DBSA, to toluenesulfinic acid, phosphenylic acid, benzoic acid, laurate and 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 heat-sensitive CTP plate with background dye can, such as 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 additives as binded reinforcing agent etc., resin bed coating weight 0.8-1.2g/m
2.
(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.Action principle is that positive image thermosensitive lithographic printing plate has after the scanning of infrared laser of data signal through semiconductor laser or YGA Laser emission, unexposed part alkali soluble resin and infrared absorbing agents and resistance solvent associate, after developing, alkaline-based developer is not removed, and exposed portion changes into heat because infrared absorbing agents absorbs infrared light, destroy the association that alkali soluble resin and infrared absorbing agents and resistance solvent occur, its dissolution velocity in alkaline-based developer is accelerated greatly, after alkaline-based developer develops, be removed.
Phenolic resins comprises linear phenolic resin and polyethylene phenol resin, and linear phenolic resin can be prepared by polycondensation reaction, and 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, face ethyl phenol, an ethyl phenol, to ethyl phenol, propyl phenoxy, normal-butyl phenol, tert-butyl phenol, 1-naphthols, beta naphthal.A minimum aldehyde or ketone.Wherein aldehyde can be formaldehyde, acetaldehyde, valeral, benzaldehyde, furfural.Ketone can be acetone, MEK, methyl n-butyl ketone, metaformaldehyde.Weight average molecular weight is determined by CPC.Be advisable with 1000 to 15000,1500 is best to 10000.Linear phenol-aldehyde resin mountain aldehyde and phenol condensation.Metacresol/paracresol/2 in phenol, 5-diphenol/3,5-diphenol/phloroglucin/mixed proportion is 40-100/0-50/0-20/0-20/0-20.Or phenol/orthoresol/paracresol/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 atoms such as iodine and fluorine, or C
1-4alkyl so that on corresponding resin with these groups.These polyethylene phenol resin are by one or more hydroxy styrenes polymerization.On it, can there is substituting group, on the aromatic ring of polyethylene phenol, be connected with C
1-4alkyl 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 absorbing agents in the present invention also not exclusively absorbs ultraviolet light, or absorb still to not sensitization of ultraviolet light, so do not affect formula under the white light that contains Weak ultraviolet.In all infrared absorbing agents, preferably following IR dyes: cyanine dye, half cyanine dye, polymethin dyes, squaraine dye (squarilium dye), crocic acid salt (crocnium dye), methine, virtue methine, polymethine, pyralium salt dyestuff, thiapyran dyestuff, naphthoquinone dyestuff, anthraquinone dye, oxazole, thiazole, merocyanine, chain cyanine, koha, naphthalene cyanines, phthalein is general, sulphur cyanines, porphyrin, indoles three carbocyanines, dislike indoles three carbocyanines, indoles is spoilt, triarylamine, polyaniline, polypyrrole, pyrazoline azo, sulfo-pyrans sub-virtue, oxazines, polythiophene, oxidation indolizine, wherein cyanine dye, polymethin dyes, pyrans anchor salt dyestuff and thiapyran dyestuff are better.The polymethin dyes in these compounds with cyanine dye and structure has absorption at 650nm to 900nm wave band.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) independently
2;
Each R
1can be alkyl, alkyl azochlorosulfonate or alkyl ammonium group independently;
R
2can be hydrogen, halogen, SR, S0
2r, OR or NR
2;
Each R
3can be hydrogen, alkyl, COOR, OR, SR, S0 independently
3 -, NR
2, halogen and not necessarily replace fused benzo ring;
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 R
1alkyl azochlorosulfonate, owing to having formed inner salt, so A
-can not exist, and alkali metal cation will be essential as counter ion.If R
1be alkyl ammonium group, will need the second anion as counter ion.The second anion can 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 the cyanine dye that contains as mentioned above cation and anion salt structure, and the mass ratio in plate coating is 3-20%, is preferably 5-10%.
3. acid agent
After infrared laser scanning, infrared absorbing agents in heat-sensitive layer and resin bed absorbs heat, there is to decompose product acid in the acid agent of exposure area, solubility property in alkaline-based developer is strengthened, in resin bed, contain IR dyes acid agent simultaneously, the heat that IR dyes absorbs is easy to conduction and causes acid agent generation acid-producing, there is certain effect of concluding in unexposed part and IR dyes, dissolubility in alkaline-based developer weakens, improved like this plate sensitivity, accelerated developing powder, improved development latitude.
Acid agent comprises all sour materials that produce after irradiation, mainly comprises drone salt, organohalogen compounds, sulphonic acid ester, 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 effect.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 are 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, CMe
2.Q 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.The effect reason of resistance solvent in formula it be unclear that.But have any to affirm, the component that is added with resistance solvent is inoperative and effective at last exposed portion at exposed portion.And can find out that in the contrast of exposed portion and last exposed portion resistance solvent has the insoluble characteristic of reinforcement.So more be conducive to form good image.The addition of resistance solvent is preferably the 2-10% of imaging layer alkali soluble resin weight.
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 should be at room temperature solid, or fusing point is the liquid of 180 degree.This compounds can be sulphonic acid ester, phosphate, and aromatic esters, aromatic sulfonic acid ester, fragrant two sulfones, carboxylic acid anhydrides, aromatic ketone, aromatic aldehyde, aromatic amine, aromatic ester, these compounds can use separately or after mixing.
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 phenethyl ester, ethyl p-toluenesulfonate, the p-methyl benzenesulfonic acid tert-butyl ester, p-methyl benzenesulfonic acid n-octyl, p-methyl benzenesulfonic acid phenyl ester, p-methyl benzenesulfonic acid 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 dimethyl sulfone.
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, Pentyl benzoate, 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, benzoyl oxide.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, diphenyl 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 link together by ester bond or hydroxyl and linear phenolic resin or polyethylene phenol resin.
Scold aqueous polymer to represent the applicable resistance solvent of another type, this base polymer be it seems by improve the developer tolerance of coating from coating repulsion wetting agent, scold aqueous polymer can add in the glue-line that comprises hydrophobic polymer, also can be used as the individual course on the glue-line of hydrophobic polymer, also can become barrier layer, heat sensing layer and developer solution shielding are come, and barrier layer can dissolve in developer solution, for example comprise the polymer of the construction unit of siloxanes and/or perfluoroalkyl, comprise phenyl methyl siloxanes 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 the control of upper and lower two layers of coatings thickness and baking temperature: resin bed is to be coated in aluminium plate support through 120 DEG C-135 DEG C after fully being dissolved by organic solvent, and 2-3min is dried film forming, and weight is 0.8-1.2g/m
2.After thermo-responsive photosphere is fully dissolved by organic solvent, at 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/m
2.
This coating may further include one or more different layers, and except following examples coating, this coating can comprise glue-line; to improve the cohesive of coating to base material, cover layer, protective finish is exempted from and is polluted or mechanical damage; photo-thermal conversion coating, it comprises infrared absorbing agents.
Support: version base can sufficient aluminium, zinc, steel or copper, or contain chromium, zinc, iron, the metallograph of aluminium.Best with aluminium plate in this formula.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 by infrared or near-infrared laser and bombardment with laser beams exposure, wave-length coverage again 800-1200nm positive image thermosensitive lithographic printing plate absorbs the light of this wave-length coverage, this exposure light source is modal exposure method, this exposure method be easy to by emission wavelength again the laser of 830nm and 1064nm realize.The effective exposure being applicable to realizes by imaging platemaking machine, as: Creo Trendsettcr (CREO Corp.British C0lumhia, Canada) and Gerber Crescent 42T (production of Gerber company).
The imaging exposure of positive image thermosensitive lithographic printing plate can be used one equipment easily, comprise a thermal print head, imaging device is applicable at least connecting a thermal print head, all generally a branch of thermal print head, if TDK No.LV5416 is as in hot facsimile machine and heat sublimation printing machine.When by thermal head imaging exposure, positive image thermosensitive lithographic printing 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, and as RIP can accept the page number descriptive language of 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 the exposure area of photosensitive layer, and unexposed region can not be permeated and dissolve.The developer solution of tradition lithographic printing plate plate is all with sig water, by plate is carried out to development treatment, just leaves the camegraph of the slight projection of the oleophylic that has no the formation of light sensation photosphere on the space of a whole page.Can the photosensitive layer of non-image part, remove from the space of a whole page after development completely, depends on the dissolubility of photosensitive layer to diluted alkaline.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, sodium metasilicate, potassium silicate etc.Protective agent also claims inhibitor, can stablize developer solution performance, can reduce developer in the little etch to version base of developing process simultaneously, 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 the surface tension that reduces developer solution, makes developer solution can soak quickly and evenly the space of a whole page, is beneficial to the uniformity developing.Conventional wetting agent has the agriculture such as neopelex, tween surface-active agent, is all glutinous thick liquid, and these two kinds of surfactants, except having wetability, also have the performance of emulsion dispersion, thereby in developing process, forme also helped to the function of washing.Developer solution, taking water as solvent, generally adopts deionized water.
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 sensitivity, 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, all to have stirring, in the container of condenser pipe, (preferably pass into nitrogen, get rid of oxygen in bottle), add the solvent for dissolved monomer, be generally N, dinethylformamide, then the monomer of be used for copolymerization is added to sub-fraction in proportion, and add appropriate initator (initator is the one in azo or organic peroxide), stirring and dissolving 10-20 minute.Be dissolved to solution near-transparent, begin to warm to 70-80 DEG C, react after 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 in 4 premium on currency, 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 passes into nitrogen and gets rid of oxygen in bottle, add ethyl cellosolve 200ml DMF200ml, dibenzoyl peroxide 0.6g, acrylamide 20g, start stirring and dissolving, add methacrylic 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 dissolves in 50ml ethyl cellosolve), in 1 hour, drip off, continue reaction 4 hours, after reaction finishes, 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 in 4 premium on currency, obtain white solid, filter, clean three times, be placed in 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 the formula of main film-forming resin
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/m
2.
(2) electrolysis
Require the lipophile of plate picture and text part good, blank parts hydrophily will be got well, blank parts hydrophilicity well need to be by carrying out sand screen mesh to aluminium plate, make blank sand holes part water storage and oleophylic not, the formation electrolysis of Grains, uses aluminium plate and graphite as two electrodes, in the hydrochloric acid solution of electrolyte: 6-20g/L, 50HZ alternating current, electric current 20-100A/d m
2, liquid temperature 30-60 DEG C, electrolysis time 5-90 second, controls Ra=0.5-0.6um.
(3) oxidation
For improve aluminium plate surface mechanical strength, strengthen wearability and improve hydrophily and will carry out anodized to aluminium plate surface, defend with the sulfuric acid solution of 15%-30%, at 20-60 temperature, 5-250 electrolytic treatments second, aluminium ion concentration: 0.5-5g/L, uses direct current, electric current 1-15A/d m
2. control oxide-film=2-3g/m
2.
(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, uses sodium silicate aqueous solution to soak 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/m
2be advisable, upper strata coating weight is with 0.6-0.8g/m
2.
(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), carries out the scanning plate-making of different laser energy on sample, 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 measuring 50% plain net value under different exposure energies, is 50% show value until find out in step-wedge bar 50% plain net region, and 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, from having to the sensitivity of 1: 1 that is plate without the corresponding sensitivity of critical point disappearing, also can be described as plate normal sensibility.
G) by different sensitivity plate blank spaces in test-strips after acetone titration exposure, until any obvious circle trace is can't see in blank space titration and not titration place, be 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/m 2 |
Table 6 is sensitivity testing result relatively
2, the detection of development latitude
In SCREEN8600E platemaking machine, light exposure according to 1.3 times of the value of optimum exposure obtained above is exposed, just carry test-strips and on sample, carried out the scanning plate-making of different laser energy, different developing time under 23 DEG C of development temperatures, (select 10s here, 20s, 30s, 40s) under condition, example edition is developed to process and process, (blank space is not kept on file can to make plate reach instructions for use, density OD value < 0.29, coating does not subtract film on the spot, site reduction 3-99%) the peak of developing time 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
After coating is dry, the plate of coating cuts into the square of 10 × 10cm, and 4 squares of each sample do respectively following coating performance and detect:
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 square
1, wash away coating with mixed solvent or acetone, then the W that weighs after drying
2.W
1-W
2be 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 square
1, then in ready developer solution, temperature is generally 25 DEG C of immersions 30 seconds, takes out and dries rear weigh W
2, W
1-W
2/ W
1be 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 square
1, then in ready developer solution, (TPD-3) temperature is generally 25 DEG C of immersions 60 seconds, takes out and dries rear weigh W
2, W
1-W
2/ W
1be alkali resistant loss in 60 seconds.
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 square
1, more inner at ready solvent (EC of 60% weight portion, the IPA of 40% weight portion), temperature is generally 25 DEG C and soaks 60 seconds, takes out and dries rear weigh W
2, W
1-W
2/ W
1be solvent loss in 60 seconds.
Coating performance testing result table 8
4, the detection of pressrun
Make with site, on the spot, the wear-resisting test-strips of picture and text, threading has rubber ball, diamond dust, and graining liquid (can prepare according to actual print situation oneself by graining liquid, general composition and fountain solution are similar) drum type device in grind 30-60 minute, then take out wear rib, observe the picture and text damaed cordition on it, can simply judge the pressrun of plate.Following table 9 is the abrasion condition of 30 DEG C of mills of graining 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 |
| 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 layer on support, is coated with positive heat-sensitive photosensitive layer on alkali soluble resins layer; It is characterized in that: described resin bed is made up of the hold concurrently good film-forming resin of alkali solubility and background dye and development accelerant of solvent resistance; Described film-forming 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-group and polar group; Weight average molecular weight range is between 15000-35000, and number-average molecular weight is between 7000-15000.The monomer that contains polar group accounts for the preferred 45-65% of quality percentage composition of whole synthon, and the monomer that contains acidic-group accounts for the preferred 5-25% of quality percentage composition of whole synthon.This film-forming resin is more than 95% at the quality percentage composition of resin bed.
2. the positive heat-sensitive ink of resistance to UV CTP plate according to claim 3, is characterized in that: being used for the acidic-group that the monomer of copolymerization comprises is R
1-COOH, R
2-OH, R
3at least one in-Ph-OH. described polar group is R
4-NH2, R
5-CN, R
6-CO-NH2, R
7-NH-CO-R
8, R
9at least one in-SO2-NH2.R wherein
1-R
9be independently the alkyl containing 1-9 C, aryl, aralkyl separately.
3. the positive heat-sensitive ink of resistance to UV CTP plate according to claim 1, is characterized in that: be used at least one in monomer that acidic-group that the monomer of copolymerization comprises is following structural formula:
The described monomer with polar functional group is at least one in the monomer shown in following structural formula:
4. the positive heat-sensitive ink of resistance to UV CTP plate according to claim 1, it is characterized in that: 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, and described esters monomer is at least one in the monomer shown in following structural formula:
5. the positive heat-sensitive ink of resistance to UV CTP plate according to claim 1, is characterized in that: described development chaotropic agent is any one in organic acid or acid anhydrides.The quality percentage composition of development chaotropic agent in resin bed is 5-10%.
6. the positive heat-sensitive ink of resistance to UV CTP plate according to claim 1, it is characterized in that: described background dye is Victoria blue, alkaline bright blue, solvent blue, crystal violet, one or more in crystal violet or methylene blue, the quality percentage composition of background dye in resin bed is 1-3%.
7. the positive heat-sensitive ink of resistance to UV CTP plate according to claim 1, it is characterized in that: described resin bed is to be coated on support and to dry through 120 DEG C-135 DEG C the film that 2-3min forms after described component is fully dissolved in organic solvent, and rete weight is 0.8-1.2g/m
2.
8. the positive heat-sensitive ink of resistance to UV CTP plate according to claim 1, is characterized in that: described plate support is the processing of process electrochemistry graining, tegmen oxidation processes, the aluminum plate foundation of sealing of hole processing.
9. the positive heat-sensitive ink of resistance to UV CTP plate according to claim 1, is characterized in that: described positive heat-sensitive photosensitive layer comprises: film-forming resin, and IR dyes, thermic produces acid source, hinders molten dissolution compound, illuminating colour; Described film-forming resin is linear phenolic resin, and weight average molecular weight is 5000-20000, M
w/ M
nfor 1.5-2.0, the quality percentage composition of film-forming resin in photosensitive layer is 40-80%.
10. the positive heat-sensitive ink of resistance to UV CTP plate according to claim 8, is characterized in that: it is drone salt that described thermic produces acid source, organohalogen compounds, and sulphonic acid ester, triazines and sulfohydrazide hydrazone class are produced at least one in acid source; The molten dissolution compound of described resistance is sulphonic acid ester, at least one in carboxylic acid ester compound; Described photosensitive layer is to be coated on resin bed after described component is fully dissolved in organic solvent, and through 120 DEG C-135 DEG C, 2-3min is dried the film forming, and weight is 0.5-0.9g/m
2.
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| CN112638657A (en) * | 2018-08-31 | 2021-04-09 | 富士胶片株式会社 | Lithographic printing plate precursor, method for producing lithographic printing plate, lithographic 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 |
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