CN110007564A - A kind of positive-working lithographic printing plate precursor of multicoat sensitive for infrared radiation and the method for forming image - Google Patents
A kind of positive-working lithographic printing plate precursor of multicoat sensitive for infrared radiation and the method for forming image Download PDFInfo
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- CN110007564A CN110007564A CN201910086321.0A CN201910086321A CN110007564A CN 110007564 A CN110007564 A CN 110007564A CN 201910086321 A CN201910086321 A CN 201910086321A CN 110007564 A CN110007564 A CN 110007564A
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- printing plate
- infrared radiation
- plate precursor
- lithographic printing
- sensitive
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
Abstract
The present invention provides a kind of positive-working lithographic printing plate precursor of sensitive for infrared radiation, the Lighographic printing plate precursor includes :(a) base, (b) are covered on inner coating above base, (c) is covered on the external coating above inner coating.The inner coating includes a kind of repetitive unit derived from maleimide monomer and the polymeric binder P for dissolving in alkaline-based developer, and wherein other repetitive units except maleimide are derived from acidity coefficient pKaPolymerisable monomer greater than 8；The external coating is comprising a kind of infrared radiation absorption compound and is different from internally coated another polymer adhesive Q.Being designed so that the Lighographic printing plate precursor not only can be the radiosensitive of 700 ~ 1200 nm to maximum wavelength, and it is made can imaged printing form precursor also there is good resistance to chemical solvent, the phenomenon that being not susceptible to printed chemical attack, dissolution in use, to be conducive to extend the service life of lithographic printing plate.
Description
Technical field
The invention belongs to offset lithography printing plate fields, and in particular to a kind of positive working lithographic of sensitive for infrared radiation
Plate precursor.The present invention also relates to the methods for using the precursor to obtain lithographic printing plate.
Background technique
The imageable element for being used to prepare lithographic plate, which generally comprises, is applied to carrier water-wetted surface (or middle layer)
On one or more imageable layers, which includes one or more dispersion radiation-sensitive ingredients in a binder.
After radiant image, the exposure area of imageable layer or non-exposed areas are removed by suitable developer, expose lower section
Carrier water-wetted surface.If what is removed is exposure area, imageable element if is considered as positive image plate-making, on the contrary, if
What is removed is non-exposed region, which is considered as negative image plate-making.No matter which kind of situation, in imageable layer not by
The region of removing is ink receptive, and is then that receive water or aqueous solution (logical by the water-wetted surface that developing process exposes
It is often fountain solution) and repel ink.
In the prior art the radiation-sensitive ingredient for the imageable element of positive image plate-making be usually containing novolaks or
Other novolac polymer binders and diazonium quinone optical imaging components can image forming composition.In addition to this, there are also be based on various phenolic aldehyde
Resin and infrared radiation absorption compound can image forming composition.In actual lithographic printing, common printing office chemicals
To can image forming composition have corrosion function, such as plate cleaning agents, transfer cloth detergent and fountain solution in alcohol substitute, especially
It is that used in the printing process using ultraviolet solidifiable ink have high esters, ethers or flavonoid content
Purificant.Therefore, in order to guarantee can ultraviolet curing ink normal printing, can radiosusceptibility used in image forming composition
Composition must have good erosion resisting.
However, quinone di-azido compound commonly used in the prior art and phenolic resin radiation sensitive composition dissolve in
Clean galley glycol ether solvent, be unfavorable for can ultraviolet curing ink printing.Therefore, group can be imaged by how improving
It closes object and this field technical problem urgently to be resolved is had become to the tolerance of solvent and printing office chemicals.
Summary of the invention
The technical problem to be solved in the present invention is that overcome it is existing for lithographjic platemaking can image forming composition vulnerable to print
The defect of room chemical attack is brushed, and then the IR-sensitive composition that a kind of pair of printing office chemicals has good resistance is provided
And utilize lithographic printing plate precursor made from the composition.
The technical solution of present invention solution above-mentioned technical problem are as follows:
A kind of positive-working lithographic printing plate precursor of sensitive for infrared radiation, it includes:
(a) base,
(b) inner coating being covered on above base, comprising a kind of repetitive unit derived from maleimide monomer and solvable
In the polymeric binder P of alkaline-based developer, wherein other repetitive units except maleimide are derived from acidity coefficient pKa
Polymerisable monomer greater than 8；
(b) external coating being covered on above inner coating comprising a kind of infrared radiation absorption compound and is different from internally coated another
A kind of polymeric binder Q.
The polymeric binder P that the inner coating is included is indicated by following construction formula (I):
— (A) x—(B)y—(I)
Wherein A indicate derived from maleimide monomer () repetitive unit, B indicate derived from one kind
Or it is a variety of with ethylenically unsaturated groups and acidity coefficient pKaGreater than other repetitive units of 8 polymerisable monomers；And base
In the total weight of polymeric binder P, x accounts for 3-30 weight %, and y accounts for 70-93 weight %.
And the ratio between the polymer adhesive P and inner coating total weight are 0.40:1 ~ 0.99:1, that is, it is total to account for inner coating
The 40-99 wt% of weight.
The inner coating also includes a kind of background contrast's dyestuff.With the dyestuff of high-selenium corn optionally in visible light region
All it is suitable as background contrast's dyestuff, preferably one of oil-soluble dyes and basic dye or a variety of mixing.The background pair
Than 0.1 ~ 8wt% that the additive amount of dyestuff accounts for the inner coating total weight.
The inner coating may also contain a kind of infrared radiation absorption compound.The infrared radiation absorption compound has
Wavelength absorption range 700-1200nm preferably is selected from cyanine dye, anthraquinone dye, phthalocyanine dye, quinoneimine dye or methine cyanines dye
That expects is one or more, and the additive amount of the infrared radiation absorption compound accounts for 0.1 ~ 8wt% of the inner coating total weight.
The inner coating may also contain a kind of acid agent, and the acid agent can be selected from salt, triazine, acid anhydrides, diazonium
One of naphthoquinone sulfonic acid ester is a variety of, and the additive amount of the acid agent accounts for 0.1 ~ 10wt% of the inner coating total weight.
The inner coating may also contain another polymeric binder P1, the polymeric binder P1 can be selected from phenol
Aldehyde resin, polystyrene derivative, polyurethane and different from one of polyacrylic acid (ester) of polymeric binder P or more
Kind, the additive amount of the polymeric binder P1 accounts for 1 ~ 40wt% of the inner coating total weight.
The external coating includes at least one with infra-red radiation of the wavelength absorption range between 700-1200nm
Absorption compound preferably is selected from one kind or more of cyanine dye, anthraquinone dye, phthalocyanine dye, quinoneimine dye or methine cyanine dyes
Kind, the additive amount of the infrared radiation absorption compound accounts for 0.5 ~ 10wt% of the external coating total weight
The external coating includes a kind of polymeric binder Q, can be derived from phenolic resin, poly- (hydroxy styrenes), polyurethane
With one of polyacrylic acid (ester) or a variety of, the additive amount of the polymeric binder Q account for the external coating total weight 80 ~
99.5wt%。
The external coating may also contain a kind of dissolution inhibitor, and the dissolution inhibitor can be selected from triarylmethane dye
One of material, salt, ketone and ester type compound are a variety of, and the additive amount of the dissolution inhibitor accounts for the external coating total weight
0.1 ~ 20wt%.
The external coating may also contain a kind of acid agent, and the acid agent can be selected from salt, triazine, acid anhydrides, diazonium
Naphthoquinone sulfonic acid ester it is one or more, the additive amount of the acid agent accounts for 0.2 ~ 10wt% of the inner coating total weight.
The Lighographic printing plate precursor, which is characterized in that the base is through at electrolysis roughening and anodic oxidation
The aluminium base of reason.
The application method of the positive-working lithographic printing plate precursor of-kind of aforementioned sensitive for infrared radiation, which comprises A)
Aforementioned Lighographic printing plate precursor is implemented with infra-red radiation to press image exposure, is had become to be formed containing exposure and unexposed area
Element, B) contact the image-forming component with alkaline developer only to remove the exposure area, manufactured lithographic printing
Version.
It is described to be carried out by image exposure using the infrared laser of wavelength 700-1200 nm radiation, and the alkalinity is aobvious
Shadow agent is aqueous solution of the pH value less than 14.
The lithographic printing plate that the method obtains.
The term " imageable element " and " plate precursor " meaning having the same used herein.
Multi-layer imageable element of the present invention can be used there are many mode, and preferred purposes is as lithographic printing
The precursor of printing plate, it is not intended that being sole purpose of the invention.For example, imageable element of the invention can also be used to prepare
Photoresist, printed circuit board, microelectronics and micro-optic device, or there are other non-imaging application to be such as used in paint composite.
(1) component of imageable element
Imageable element of the invention generally comprises base, inner coating (also referred to as " bottom ") and is covered on outer in the inner coating
Coating (also referred to as " top layer ").Before thermal imaging, the external coating can not be removable by the alkaline developer, but after thermal imaging, described outer
Imaging (exposure) region of coating can be removable by the alkaline developer.The inner coating can also be removable by the alkaline developer.The present invention
Imageable element in there are radiation absorbing compound, the radiation absorbing compound is usually absorbing wavelength in 700-1200nm
The near-infrared radiation absorption compound of range.It is preferred that the compound all separately exists in external coating, but can also optionally all
It separately exists in inner coating, or is respectively present in external coating and inner coating simultaneously.
The base of imageable element of the invention usually has water-wetted surface, and is firm, stable, tough under conditions of use
Property and size constancy.In general, the base can be any self-supporting material, including polymer film (such as polyester, polyethylene, poly- carbon
Acid esters, cellulose ester polymer and polystyrene film), glass, ceramics, metal plate or foil or cardboard (including resin coating paper
And metallized paper) or any of these materials applications as laminates (applications as laminates of such as aluminium foil and polyester film).Metal base include aluminium,
Copper, zinc, titanium and its alloy plate or foil.
Preferred base is made of alumina supporter, and the alumina supporter can use technical treatment well known in the art, the technology packet
Include physics graining, electrochemistry graining, chemical graining and anodized.
The alumina supporter of the chemical graining and anodized can further using such as silicate, dextrin, hexafluorosilicic acid,
The alkali metal phosphate solution of alkali metal containing an ancient small-mouthed wine vessel compound (such as sodium fluoride), poly- (vinyl phosphonic acid) (PVPA), vinyl phosphonic acid are total
Polymers, poly- (acrylic acid) or acrylic copolymer processing form one layer of hydrophilic layer.The preferred graining of the present invention and anodized
Alumina supporter known procedure is handled through alkali metal phosphate solution to improve surface hydrophilicity.
The variable thickness of base, but the abrasion from printing should be enough to bear and sufficiently thin to wrap galley.It is preferred that
Embodiment include thickness 0.1-0.6 | the aluminium foil of mm.
Base can also be the cylinder for applying various layer compositions thereon and thereby the integral part for constituting printing machine.It is this kind of at
As the use of roller is described in such as United States Patent (USP) 5713287.
The inner coating of imageable element of the invention includes at least one repetitive unit derived from maleimide monomer
And the polymeric binder P for dissolving in alkaline-based developer is indicated by following construction formula (I):
— (A) x—(B)y— (I)
Wherein A indicate derived from maleimide monomer () repetitive unit, account for polymeric binder P
The 3-30% of total weight, preferably 5-20%.
B indicates there is ethylenically unsaturated groups and acidity coefficient pK derived from one or moreaGreater than 8 polymerizable lists
Other repetitive units of body, such as: (methyl) styrenic derivatives, (methyl) acrylate, (methyl) acrylamide, N- take
Generation (methyl) acrylamide, (methyl) acrylic acid cyanogen ethyl ester, (methyl) acrylonitrile, a- cyano styrene, vinylacetate, N- take
For maleimide, maleic anhydride, vinyl ketone, vinylpyridine, n-vinyl pyrrolidone, 1- vinyl imidazole, ethylene
Base carbazole and vinyl alcohol and vinyl polyalkylsilanes, optimization styrene analog derivative, (methyl) acrylate, N- replace (first
Base) acrylamide；B repetitive unit accounts for the 70-97% of polymeric binder P total weight, preferably 80-95%.
Polymeric binder P can be (such as even with known ethylenically unsaturated groups polymerisable monomer and polymerization initiator
Two isobutyl of nitrogen is fine or AIBN) and its solvent heat and oxygen barrier reaction condition under prepare.Representative synthetic method is below
It is described in embodiment.
The total amount of polymeric binder P present in inner coating composition usually accounts for the 50-99% weight of inner coating gross dry weight amount
Amount, preferably 70-98% weight.
In order to make coat colorization of the invention, a kind of background contrast's dyestuff can be added in inner coating.In visible light region
In with the dyestuff of high-selenium corn be all suitable as background contrast's dyestuff, preferably oil-soluble dyes and basic dye.Background contrast's dye
The specific example of material can be selected from crystal violet, ethyl violet, crystal violet, malachite green, brilliant green, Victoria pure blue, Victoria blue
R, victoria blue BO, rhodamine B, methylene blue, Oil Yellow 101, solvent green BG, solvent blue BOS, solvent blue 603, nigrosine
BY, nigrosine T-505, solvent be black and Japanese Patent Publication 293247/1987 described in one or more of dyestuff it is mixed
Close object.Further, it is also possible to suitably use such as phthalocyanine color, the pigment of azo pigments and titanium oxide.Based on inner coating gross weight
Amount, the additive amount of background contrast's dyestuff are 0.1 ~ 8wt%, preferably 0.1 ~ 5wt%.
The inner coating may also contain a kind of infrared radiation absorption compound, and the infrared radiation absorption compound can
It is representative selected from the one or more of cyanine dye, anthraquinone dye, phthalocyanine dye, quinoneimine dye or methine cyanine dyes
Specific descriptions when external coating part is described below in infrared radiation absorption compound.The addition of the infrared radiation absorption compound
Amount accounts for the 0.1 ~ 5wt%, preferably 0.1 ~ 3wt% of the inner coating total weight.
The inner coating may also contain a kind of acid agent, and the acid agent can be selected from salt, triazine, acid anhydrides, diazonium
One of naphthoquinone sulfonic acid ester or a variety of mixing.Acid agent is to cause to decompose the precursor for generating Bronsted acid by heat, according to electricity
The difference of negativity, acid agent can be divided into non-ionic acid agent and ionic acid agent, wherein non-ionic acid agent includes halogen
The triazine that substituted alkyl replaces, the triazine is described in United States Patent (USP) 3,779,778, such as bis- (three chloromethanes of 2- phenyl -4,6-
Base) s-triazine, 2, bis- (trichloromethyl) s-triazine of 4,6- tri- (trichloromethyl) s-triazine, 2- methyl -4,6-；Non-ionic production acid
Agent further includes the acid anhydrides of organic acid, such as acetic anhydride, phthalic anhydride, tetrabydrophthalic anhydride, hexahydrophthalic acid
Acid anhydride, maleic anhydride, pyromellitic acid anhydride.Ionic acid agent includes salt, for example, cation be iodine, Liu, Phosphonium,
Oxygroup sulfoxonium (oxysulphoxonium), oxygroup sulfonium (oxysulphonium), quaternary ammonium salt, diazonium, Huo Arsenic
Salt, common salt include diphenyl iodnium, triphenyl sulfonium salt, Arenediazonium salts, tetraalkyl ammonium salt, four aryl quats
Acid agent described in salt, amino acid inner salt and United States Patent (USP) 6787281,5491046,7217499,7033722.The present invention
Preferred acid agent such as triazine D (CAS No 42573-57-9, available from Sigma-Aldrich) Irgacure 250,
Irgacure 270 (available from BASF Corporation), WPI-116, WPI-169(are available from FUJIFILM Wako
Pure Chemical Corporation).The additive amount of the acid agent accounts for 0.1 ~ 10wt% of the composition total weight,
Preferably 1 ~ 5wt%.
The inner coating may also contain another polymeric binder P1, the polymeric binder P1 can be selected from changing
Property phenolic resin, polystyrene derivative, polyurethane and different from one of polyacrylic acid (ester) of polymeric binder P or
It is a variety of, it is however generally that, from the perspective of never weakening imageable element sensibility, polymeric binder is usually alkali solubility polymerization
Object, currently preferred polymeric binder P1For phenolic resin or different from the polyacrylic acid (ester) of polymeric binder P.Institute
The additive amount for stating binder accounts for 1 ~ 40wt% of the composition total weight, preferably 1 ~ 20wt%.
In addition to this, inner coating composition of the present invention can also include in usual amounts various additives, such as divide
Powder, moisturizer, biocide, plasticizer, the surfactant for coatability or other performance, tackifier, filler and
Incremental agent, pH adjusting agent, desiccant, defoaming agent, preservative, antioxidant, development promoter, rheology modifiers or they
Combination, or it is usually used in any other additives of lithography technique.
The overcoat compositions include infrared radiation absorption compound, wavelength absorption range in the present invention
600-1400 nm, the preferably radiation of 700-1200nm.Compound (sometimes referred to as " photothermal conversion materiat " or " thermal transition
Agent ") it absorbs radiation and is translated into heat.The compound can be dyestuff, carbon black or pigment, preferred coloring agent, more preferable near-infrared
Absorb cyanine dye.The example of available pigment is that ProJet 900, ProJet 860 and ProJet 830 (can be certainly
Zeneca Corporation is obtained).Available carbon black compound such as FX-GE-003 (Nippon Shokubai production) or
Carbon black through anionic group surface functionalization such as CAB-O-JET 200 or 300 (Cabot of CAB-O-JET
Corporation production).The example of suitable dyestuff includes but is not limited to cyanine dye, anthraquinone dye, phthalocyanine dye, quinone Asia
Amine dyestuff, azo dyes, squaraine dye, crocic acid ester dyestuff, triarylamine dyes, thiazole (thiazolium) dyestuff, indoles
(indolium) dyestuff, oxonol dye, oxazole (thmzolmm) dyestuff, indole cyanine dyes, indole aniline (indoaniline)
Dyestuff, indole tricarbonyl dyestuff, three carbonyl cyanine dyes of oxa-, thiocyanine (thiocyanine) dyestuff, three carbocyanine of thia
(thiatricarbocyanine) dyestuff, merocyanine dyes, cryptocyanine dye, naphthalene cyanine dyes, polyaniline dye, polypyrrole dye
One of material, polythiophene dye, oxazine dye, naphthoquinone dyestuff, methine dyes, porphyrin dye are a variety of.Other suitable dyes
It includes United States Patent (USP) 6294311 and 5208135 and references cited therein that material, which can be described in numerous publications,.
Common near infrared absorption cyanine dye can be described in such as United States Patent (USP) 6309792,6264920 and of United States Patent (USP)
In United States Patent (USP) 6787281.Suitable dyestuff can be formed or can be obtained from extensive stock source with conventional method and starting material,
For example derive from the IRD-85 and IRD-67 of DKSH company.
Except low molecular weight IR- absorb dyestuff in addition to, it is possible to use the IR dye moiety with polymer ining conjunction with, that is, use IR dyestuff sun from
Son is to include carboxyl, sulfo group, phosphoryl (phosphor) or phosphono in ionic means and polymer lateral chain
(phosphono) the IR dye salt absorbing material of functional group's interaction.
Infrared radiation absorption compound can usually account for the amount of the 0.1%-10wt%, preferably 1-6wt% of external coating total weight
In the presence of.Those skilled in the art can easily determine the specific dosage of infrared radiation absorption compound.
Overcoat compositions in the present invention also include a kind of polymeric binder Q, and having been used for multilayer in prior document can
Any polymeric binder in the outer layer of thermal imaging element is used equally for the topcoating composition in imageable element of the invention
Object.The polymeric binder Q can be derived from phenolic resin, poly- (hydroxy styrenes), polyurethane and polyacrylic acid (ester)
It is one or more.
It is preferred that polymeric binder Q in external coating be it is not soluble in water and dissolve in alkaline developer containing multiple phenolic hydroxyl groups
Phenolic resin, or containing other polymer of one or more phenolic hydroxyl groups on main chain or in side group.Such as line style phenolic aldehyde tree
Rouge, resol, the side group containing phenolic group acrylic resin and polyvinyl phenol resin, preferred phenolic resin.More preferable line
Type phenolic resin.
Linear phenol-aldehyde resin is commercially available and is well known in the art.Linear phenol-aldehyde resin usually passes through phenol such as Ben Ban, Yue
Phenol, neighbour Yue phenol, the condensation to Yue phenol etc. and aldehyde such as formaldehyde, poly Yue aldehyde, acetaldehyde etc. or ketone such as acetone in presence of an acid catalyst
Reaction preparation.Weight average molecular weight is usually 1000 to 30000.Typical linear phenol-aldehyde resin includes such as phenol-formaldehyde tree
Rouge, Yue phenol-Yue urea formaldehyde, phenol-Yue resinox, p-tert-butylphenol-formaldehyde resin and pyrogallol-acetone tree
Rouge.Particularly useful linear phenol-aldehyde resin by using condition well known to those skilled in the art make metacresol, metacresol with it is right
The mixture or phenol of cresols react preparation with formaldehyde.
The example of the polymer of common hydroxyl includes EP0090G, EP0010A (ASAHI YUKIZAI
Corporation)；ALNOVOL SPN452, SPN465, SPN400, (Clariant GmbH)；DURITE PD140A,
PD1632, PD494A, PD1615 (Borden Chemical, Inc.)； BAKELITE 9900,6564LB, 6866LB03
(Bakelite AG).It is preferred that useful polymer be the following examples described in EP0090G, DURITE PD494A and
DURITE PD140A。
In addition to above-mentioned phenolic resin or above-mentioned phenolic resin is replaced, external coating can also contain non-phenol polymer material as film forming
Base material.Such non-phenol polymer material include from Ma Lai Suan yu and one or more styrene monomers (i.e. styrene and
Have the styrenic derivatives of various substituent groups on phenyl ring) polymer that is formed, (Yue yl) acrylate and one or more contain
The polymer and its mixture that the monomer of carboxyl is formed.Polymer derived from maleic anhydride generally comprises 1-50% mole percent
From the repetitive unit of maleic anhydride, remaining repetitive unit other polymerisable monomers derived from styrene monomer and optionally.
The polymer formed derived from (Yue yl) acrylate and carboxylic monomer generally comprises 80-98% moles of (methyl) acrylic acid
The repetitive unit of ester.Carboxylic repetitive unit can be derived from such as acrylic acid, Yue base acrylic acid, itaconic acid, maleic acid and sheet
Well known similar monomer in field.
Hydroxystyrene polymers can also be used in polymeric binder in external coating, such as containing derived from 4- hydroxy benzenes second
The repetitive unit of alkene.
The additive amount of the polymeric binder Q accounts for 80 ~ 99.5wt% of the external coating total weight, preferably 80-98% weight
The amount of amount is present in external coating.
Topcoating composition in the present invention is also possible to selection and includes a kind of dissolution inhibitor, it usually has polar functional
Group is considered as the acceptor site with the hydroxyl Hydrogenbond of such as polymeric binder Q.Most common dissolution inhibition
Agent be triarylmethane dye for example crystal violet, ethyl violet, crystal violet, peacock green, brilliant green, victoria blue B, victoria blue R,
One or more mixtures of victoria blue BO, BASONYL purple 610.These compounds can also be aobvious as external coating simultaneously
The background dye of color.
The compound of positive electricity containing lotus (i.e. quaternized) nitrogen-atoms also is used as dissolution inhibitor, such as tetra-allkylammonium chemical combination
Object, quinoline (quinolinium) compound, benzothiazole (benzothiazolium) compound, pyridine
(pyridinium) compound and imidazoles (imidazolium) compound.Representative tetraalkyl ammonium dissolution inhibitor chemical combination
Object includes 4-propyl bromide, tetraethylammonium bromide, 4-propyl ammonium chloride, tetramethyl alkyl ammomium chloride and trimethyl alkyl bromination
Ammonium such as trimethyl octyl ammonium bromide and trimethyldecyl ammonium chloride.Representative quinoline dissolution inhibition immunomodulator compounds include 1- second
Base -2- methylpyridinium iodide quinolinium；Representative benzothiazole compound includes 3- Ethyl-2-Methyl iodate benzothiazole.
Diazonium salt also is used as dissolution inhibition immunomodulator compounds comprising for example replaces with unsubstituted diphenylamine diazonium salt such as
Methoxy-substituted diphenylamine diazonium hexafluorophosphate.There are also the representatives that ester type compound also is used as dissolution inhibition immunomodulator compounds
Property sulphonic acid ester includes the just own ester of ethyl benzenesulfonat, benzene sulfonic acid, to Yue ethyl benzenesulfonat, the p-methyl benzenesulfonic acid tert-butyl ester and to toluene sulphur
Acid phenenyl ester；Representative phosphate includes trimethyl phosphate, triethyl phosphate and tricresyl phosphate.Available sulfone includes containing virtue
Those of base such as diphenyl sulphone (DPS).
Another kind comprising polar group and play the role of dissolution inhibitor polymer material be part phenolic hydroxyl group
It is converted into sulphonic acid ester (preferably benzene sulfonate or p-methyl benzenesulfonic acid ester).There are also the derivatization phenolic aldehyde trees of the functional group containing diazo naphthoquinone
Rouge.The diazo naphthoquinone compound of polymerization includes by the reactive derivatives of the part containing diazo naphthoquinone and containing suitable reactive group
The derivatization resin formed such as the reaction of the polymer material of hydroxyl or amino.The chemical combination of phenolic resin group containing diazo naphthoquinone
The derivatization of object is well known in the art and is described in such as United States Patent (USP) 5,705,308 and 5,705,332.It is other available
Solvent inhibitor compound be described in such as United States Patent (USP) 5,705,308,6,060,222 and 6,130,026.Work as external coating
In there are the 0.1-20 wt % for when dissolution inhibition immunomodulator compounds, usually accounting for external coating gross weight, preferably 1-15 wt %.
External coating of the present invention may also contain a kind of acid agent, the acid of production described in the optional inner coating of acid agent
One or more mixing of agent, the additive amount of the acid agent account for 0.1 ~ 10wt% of the external coating total weight, preferably 1-5 wt
%。
In addition to this, external coating of the present invention can also include various additives, such as surface-active in usual amounts
Agent, levelling agent, dispersing aid, wetting agent, biocide, tackifier, desiccant, defoaming agent, preservative, antioxidant.Coating
Surfactant and levelling agent are particularly useful.
(2) preparation method of imageable element
Lithographic printing plate precursor of the present invention be by above-mentioned inner coating be coated in the base carrier on, again will be above-mentioned
External coating coating be made on the undercoating layer.Specifically, being to disperse or dissolve the inner coating and external coating respectively
In suitable coating solvent, and using suitable equipment and program such as rotary coating, blade coating, intaglio plate coating, mouth mold formula
Coating, slot coated, pull-rod coating, wire rod coating, dip coated, roller coating or extruder hopper coating, the inner coating solution is applied to
On the surface of base carrier, by drying and removing internally coated solvent in 70 ~ 160 DEG C of baking ovens, then by the external coating solution
It is applied on internally coated surface, is put down again by the solvent of external coating is dried and removed in 70 ~ 160 DEG C of baking ovens to get described
Version printing printing plate precursor.Internally coated coverage rate is usually 0.3-3.5g/m2, preferably 0.5-2.5g/m2；The coverage rate of external coating
Usually 0.1-3.5g/m2, preferably 0.3-1.8g/m2。
Wherein it is described coating solvent selection depend on the IR radiation-sensitive composition in polymeric binder and
The property of other components, usually using condition well known in the art and technology, using including acetone, methyl ethyl ketone, diethyl
Base ketone, methyl iso-butyl ketone (MIBK), ethylene glycol, 1- methoxy-2-propanol, 2- ethyoxyl-ethyl alcohol, methyl lactate, γ-fourth lactones, 1,
One of 3- dioxolane, tetrahydrofuran and water are a variety of.
Imageable element actually of the invention can have any form, including but not limited to printing block precursor, print
Brush roller, printing sleeve and printer belt (including flexible printing web).Preferably, imageable element of the invention is to be used to form
The lithographic printing plate precursor of lithographic printing plate.
(3) imaging and development of imageable element
For embodiment of the present invention, for the laser of lithographic printing plate precursor exposure of the invention to can be two
Pole pipe laser, reason are that diode laser system has high reliability and low maintenance, other laser also can be used for example
Gas or Solid State Laser.Power, intensity and the combination of time for exposure of laser imaging are apparent to those skilled in the art
's.The launch wavelength of high-performance laser used in current commercially available picture number code platemaking machine or laser diode is 800 ~
850nm, imaging device are configurable to flat logger or drum recorder, wherein imageable element be installed to it is bulging interior or
Outer cylinder surface.Preferred imaging device can from Eastman Kodak Company (Rochester, New York,
USA) with the acquisition of model Kodak Trendsetter Q800 image reproduction machine, the near-infrared containing launch wavelength 830nm
The laser diode of radiation；Other optional imaging sources include Screen Holdings Co., Ltd. (Kamigyo-ku,
Kyoto, Japan) the series of PlateRite 4300 or 8600 etc. serial plate-making picture platemaking machine.It is general that energy is imaged
Can be within the scope of 50-500mJ/cm2, preferably imaging energy is lower than 250mJ/cm2, most preferably less than 150mJ/cm2.
Although laser imaging is preferred in the practice of the invention, imaging can be by provide thermal energy by image mode
Any other measure provides.For example, imaging can be with thermal resistance head with usually said " thermally printed " and such as thermal fax machines and distillation
Used completion in printing machine, such as described in United States Patent (USP) 5488025.
It includes the standard that the sub-image of (exposure) and unimaged (unexposed) region is imaged that the imaging process of imageable element, which generates,
Then quasi- image-forming component is rinsed the outer painting for removing exposure area by image-forming component by using suitable alkaline developer solution
Layer and inner coating below and expose the water-wetted surface of base.More particularly, develop time of progress should be enough to remove exposure
The external coating and inner coating in region remove the coating of unexposed area without being long enough to.Therefore, it is " positive which is
Scheme ".
In embodiments of the invention, the pH value of such aqueous base developers aqueous solution is generally at least 9, preferably extremely
It is less 11.The optional alkaline developer solution of the present invention includes that DV-T, DV-T1, DV-PT (can be from Zhejiang Kang Erda new materials
Limited liability company obtain), GOLDSTAR Developer, GOLDSTAR Plus Developer, GOLDSTAR Premium
Developer, K300, K400 (can obtain from Eastman Kodak Company) and THD-200 (can be obtained from Agfa
), these alkaline developer solutions also typically include surfactant, chelating agent and for example inorganic metasilicic acid of various alkaline agents
Salt, organic metasilicates, hydroxide and carbonate.
Alkaline developer solution usually also includes one or more organic solvents miscible with water.It is available organic molten
Agent includes the reaction product of phenol Yu ethylene oxide and propylene oxide, such as glycol ethyl ether, ethylene glycol butyl ether, propylene glycol list first
Ether, glycerine (ether) etc..Organic solvent usually exists with the amount of the 0.5-15% of the total developer weight of Zhan.It is representative based on molten
The alkaline developer of agent includes that ND-1 developer, 955 developers and 956 developers (can be bought from Eastman Kodak Company
To).
After imageable element development, the imageable element can be washed with water and dried in any suitable manner, may be used also
With with conventional gum-solution, preferably Arabic gum handles its element, the element after imaging can also be placed in baking box into
Row baking processing, toasts 7 ~ 10 minutes, or toasted 30 minutes such as at 220 ~ 240 DEG C at 120 DEG C, can further improve in this way
The running life of resulting image-forming component.
It will finally be printed on printing surface that ink and fountain solution are coated to imageable element on lithographic offset machine
Brush, by the way that image-forming component is unexposed or unremoved area absorbs ink, and exposure area and substrate that is subjected to development and exposing
The water-wetted surface of carrier absorbs dampening solution, then by the printing ink transfer to suitable reception material such as cloth, paper, metal, glass
" transfer cloth " roller or on plastics, also can be used to be transferred to ink from imageable element and receive on material.
Compared with prior art, above-mentioned technical proposal of the invention has the advantages that
1, by design polymeric binder P, so that imageable element of the invention can be within the scope of 700 ~ 1200nm in wavelength
It is radiosensitive, it is a kind of excellent radiosensitive positive-working lithographic printing plate precursor.The lithographic printing plate made of the precursor
To isopropanol erosion have excellent resistance, therefore using IR-sensitive composition of the present invention be prepared can
Image-forming component, the phenomenon that printed chemical attack is not susceptible in printing process, is dissolved, to be conducive to extend lithographic plate print
Stencil the service life of plate precursor.
2, imageable element of the present invention is using the double-deck coating technique.Compared to single coating product, advantage exists
It is separated into respective coating in by the function of resin, the solvent resistance for improving imageable layer to the maximum extent can be with photosensitive speed
Degree.
Specific embodiment
Technical solution of the present invention is described more specifically below in conjunction with embodiment, it is clear that described implementation
Example is a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, ordinary skill
Personnel's every other embodiment obtained without making creative work, shall fall within the protection scope of the present invention.
In addition, technical characteristic involved in invention described below different embodiments is as long as they do not conflict with each other
It can be combined with each other.There is provided the following examples is to be not intended to limit this hair in any way in order to illustrate implementation of the invention
It is bright.
The following are the synthetic examples of polymeric binder P, to be expressed as according to synthetic example sequence convenient for difference
Polymeric binder PB-1, polymeric binder PB-2 ... .. etc.:
The synthesis of 1 polymeric binder PB-1 of synthetic example:
8.0 grams of maleimides, 6.0 grams of p- hydroxyphenylacrylamdies and 110 grams of glycol monoethyl ethers are added to assembly
There are more mouthfuls of round bottoms of the 250ml of heating mantle, temperature controller, mechanical agitator, condenser, constant pressure funnel and import and export of nitrogen
In flask.Constant pressure funnel equipped with 0.4 gram of AIBN be dissolved in 10 grams of glycol monoethyl ethers, 10.0 grams of methyl methacrylates,
Mixed liquor in 4.0 grams of styrene, 12 grams of acrylonitrile.The mixture in flask is heated to 65 under nitrogen protectionoC, and open
The monomer mixed solution for beginning to be added dropwise in constant pressure funnel adds for about 30 minutes into flask, and it is small that continuation is stirred to react 5 at such a temperature
When.It adds into 0.2 gram of AIBN, continues in nitrogen protection and 70 o15 hours are stirred to react under C.By reaction mixture after cooling
The methanol (adding 4 drop concentrated hydrochloric acids) being added drop-wise in 800 grams of stirrings is inner.The solid being precipitated out places into 500 grams after collected by suction
Cold water in stir 15 minutes.Collected by suction is placed on filter paper and spreads out air dried overnight, finally dries in 45 degree of baking ovens.Yield
32 grams of yellowish solids.
The synthesis of 2 polymeric binder PB-2 of synthetic example:
By 4.0 grams of maleimides, 6.0 grams of acrylonitrile, 7.0 grams of ethyl methacrylate, 3 grams of N- phenyl methyl acryloyls
Amine, 0.2 gram of AIBN and 60 gram of glycol monoethyl ether are added to and are equipped with heating mantle, temperature controller, mechanical agitator, condenser
In tetra- neck round-bottom flask of 250ml of import and export of nitrogen.Reaction mixture is heated to 65 under nitrogen protectionoThen C exists
It is stirred to react at this temperature 5 hours.It adds into 0.1 gram of AIBN, continues in nitrogen protection and 70 o15 hours are stirred to react under C.
The methanol (adding 2 drop concentrated hydrochloric acids) that reaction mixture is added drop-wise in 400 grams of stirrings after cooling is inner.The solid being precipitated out is through filtering
After collection, places into 250 grams of cold water and stir 15 minutes.Collected by suction is placed on filter paper and spreads out air dried overnight, finally 45
It is dried in degree baking oven.15.2 grams of yellowish solids of yield.
The synthesis of 3 polymeric binder PB-3 of synthetic example:
By 4.0 grams of maleimides, 6.0 grams of acrylonitrile, 4.0 grams of butyl methacrylates, 2.0 grams of N, N- diformazan methyl-prop
Acrylamide, 4.0 grams of caprolactams, 0.2 gram of AIBN and 60 gram of n,N-dimethylacetamide are added to and are equipped with heating
Set, temperature controller, mechanical agitator, condenser and import and export of nitrogen tetra- neck round-bottom flask of 250ml in.Under nitrogen protection
Reaction mixture is heated to 65oThen C is stirred to react 5 hours at such a temperature.It adds into 0.1 gram of AIBN, continues in nitrogen
Gas shielded and 70 o15 hours are stirred to react under C.The methanol that reaction mixture is added drop-wise in 400 grams of stirrings (is added 2 after cooling
Drip concentrated hydrochloric acid) it is inner.The solid being precipitated out is placed into 250 grams of cold water and is stirred 15 minutes after collected by suction.It filters and receives
Collection, is placed on filter paper and spreads out air dried overnight, finally dry in 45 degree of baking ovens.15.9 grams of yellowish solids of yield.
The synthesis of 4 polymeric binder PB-4 of synthetic example:
4.0 grams of maleimides, 6.0 grams of acrylonitrile, 4.0 grams of methyl methacrylates, 2.0 grams of styrene, 1.0 grams of N- are different
Propylacrylamide, 3.0 grams of acryloyl morpholines, 0.2 gram of AIBN and 60 gram of glycol monoethyl ether be added to be equipped with heating mantle,
Temperature controller, mechanical agitator, condenser and import and export of nitrogen tetra- neck round-bottom flask of 250ml in.Under nitrogen protection will
Reaction mixture is heated to 65oThen C is stirred to react 5 hours at such a temperature.It adds into 0.1 gram of AIBN, continues in nitrogen
Protection and 70 o15 hours are stirred to react under C.The methanol that reaction mixture is added drop-wise in 400 grams of stirrings (is added into 2 drops after cooling
Concentrated hydrochloric acid) it is inner.The solid being precipitated out is placed into 250 grams of cold water and is stirred 15 minutes after collected by suction.Collected by suction,
It is placed on filter paper and spreads out air dried overnight, finally dried in 45 degree of baking ovens.16.0 grams of yellowish solids of yield.
The synthesis of 5 polymeric binder PB-5 of synthetic example:
By 5.0 grams of maleimides, 4.0 grams of acrylonitrile, 4.0 grams of methyl methacrylates, 2.0 grams of Methacrylamides,
5.0 grams of phenyl maleimides, 0.2 gram of AIBN and 60 gram of n,N-dimethylacetamide are added to and are equipped with heating mantle, temperature control
Device processed, mechanical agitator, condenser and import and export of nitrogen tetra- neck round-bottom flask of 250ml in.It is under nitrogen protection that reaction is mixed
It closes object and is heated to 65oThen C is stirred to react 5 hours at such a temperature.Add into 0.1 gram of AIBN, continue in nitrogen protection and
70 o15 hours are stirred to react under C.Reaction mixture is added drop-wise to the methanol (adding 2 drop concentrated hydrochloric acids) in 400 grams of stirrings after cooling
In.The solid being precipitated out is placed into 250 grams of cold water and is stirred 15 minutes after collected by suction.Collected by suction is placed on filter paper
On spread out air dried overnight, finally dried in 45 degree of baking ovens.16.3 grams of light yellow solids of yield.
The synthesis of 6 polymeric binder PB-6 of synthetic example:
By 4.0 grams of maleimides, 4.0 grams of styrene, 2.0 grams of methacrylonitriles, 6.0 grams of methyl methacrylates, 4.0
Gram N- hydroxyphenyl-maleimides, 0.2 gram of AIBN and 60 gram of glycol monoethyl ether, which are added to, is equipped with heating mantle, temperature control
Device, mechanical agitator, condenser, constant pressure funnel and import and export of nitrogen tetra- neck round-bottom flask of 250ml in.In nitrogen protection
It is lower that reaction mixture is heated to 65oThen C is stirred to react 5 hours at such a temperature.It adds into 0.1 gram of AIBN, continues
Nitrogen protection and 70 o15 hours are stirred to react under C.The methanol that reaction mixture is added drop-wise in 400 grams of stirrings (is added after cooling
2 drop concentrated hydrochloric acids) it is inner.The solid being precipitated out is placed into 250 grams of cold water and is stirred 15 minutes after collected by suction.It filters and receives
Collection, is placed on filter paper and spreads out air dried overnight, finally dry in 45 degree of baking ovens.16.7 grams of light yellow solids of yield.
The synthesis of 7 polymeric binder PB-7 of synthetic example:
By 4.0 grams of maleimides, 11.0 grams of p- sulfonamide Phenyl Acrylamides, 5.0 grams of p- hydroxyphenylacrylamdies,
0.2 gram of AIBN and 60 gram of glycol monoethyl ether be added to be equipped with heating mantle, temperature controller, mechanical agitator, condenser and
In tetra- neck round-bottom flask of 250ml of import and export of nitrogen.Reaction mixture is heated to 65 under nitrogen protectionoC, then at this
At a temperature of be stirred to react 5 hours.It adds into 0.1 gram of AIBN, continues in nitrogen protection and 70 o15 hours are stirred to react under C.It is cold
But the methanol (adding 2 drop concentrated hydrochloric acids) reaction mixture being added drop-wise in 400 grams of stirrings afterwards is inner.The solid being precipitated out is received through filtering
After collection, places into 250 grams of cold water and stir 15 minutes.Collected by suction is placed on filter paper and spreads out air dried overnight, finally at 45 degree
It is dried in baking oven.17.1 grams of light yellow solids of yield.
The synthesis of 8 polymeric binder PB-8 of synthetic example:
By 4.0 grams of maleimides, 3.0 grams of p- hydroxyphenylacrylamdies, 4.0 grams of methyl vinyl ketones, 3.0 grams of benzene
Ethylene, 6.0 grams of acrylonitrile, 0.2 gram of AIBN and 60 gram of glycol monoethyl ether are added to and are equipped with heating mantle, temperature controller, machine
In tetra- neck round-bottom flask of 500ml of tool blender, condenser and import and export of nitrogen.Reaction mixture is heated under nitrogen protection
To 65oThen C is stirred to react 5 hours at such a temperature.It adds into 0.1 gram of AIBN, continues in nitrogen protection and 70 oIt is stirred under C
Mix 15 hours of reaction.The methanol (adding 2 drop concentrated hydrochloric acids) that reaction mixture is added drop-wise in 400 grams of stirrings after cooling is inner.Precipitating
Solid out is placed into 250 grams of cold water and is stirred 15 minutes after collected by suction.Collected by suction is placed on filter paper and spreads out
Air dried overnight is finally dried in 45 degree of baking ovens.16.0 grams of yellowish solids of yield.
The following are the embodiments for preparing Lighographic printing plate precursor, to be respectively indicated according to synthetic example sequence convenient for difference
For Lighographic printing plate precursor PP -1, Lighographic printing plate precursor PP -2 ... .. etc.:
Imageable element embodiment 1 prepares Lighographic printing plate precursor (PP-1)
(1) 0.50 gram of polymeric binder PB-1 and 0.01 gram of victoria blue BO inner coating: are dissolved in 6.5 grams of ethylene glycol
Single ether, 2.0 grams of butanone-2s, 0.5 gram of butyrolactone and 0.5 gram of water solvent mixture in.It will be upper using rotating coating
It states composition solution to be coated on the aluminum substrate obtained through electrochemistry roughening and anodized, then in 145 DEG C of baking ovens
It is 3 minutes dry, obtain 1.2 grams/m2Inner coating weight.Inner coating soaking is at isopropanol 1 minute without significantly dissolving or taking off
It falls, shows its excellent anti-alcohol ability.
(2) external coating: by 0.23 gram of EP0090G, 0.23 gram of PD494A, 0.02 gram of IRD-85 and 0.02 gram of crystal violet
It is dissolved in the solvent mixture of 5.8 grams of propylene glycol monomethyl ethers and 3.8 grams of butanone-2s.Using rotating coating by the combination
It is then 3 minutes dry in 145 DEG C of baking ovens in object solution coating to above-mentioned inner coating, obtain inner coating and external coating gross weight
Amount is about 2.1 grams/m2Lighographic printing plate precursor (PP-1).
The Lighographic printing plate precursor (PP-1) that the present embodiment is prepared is in 800 Quantum-II type CTP system of Kodak
830nm laser is used on version machine, drum rotating speed 220rpm, laser power 12W are scanned exposure.Original after exposure
Version is used Konita DV-T developing liquid developing 35 seconds at 25 DEG C, the exposed portion of obtained Lighographic printing plate precursor after development
Coating dissolution completely, rather than the coating of exposed portion retain.Image clearly, clear-cut margin are neat.
Imageable element embodiment 2 prepares Lighographic printing plate precursor (PP-2)
(1) inner coating: by 0.50 gram of polymeric binder PB-2,0.005 gram of IRD-85,0.01 gram of WPI-169 and 0.01 gram of dimension
The solvent that more Leah indigo plant BO are dissolved in 6.5 grams of ethylene glycol monoethyl ethers, 2.0 grams of butanone-2s, 0.5 gram of butyrolactone and 0.5 gram of water is mixed
It closes in object.Above-mentioned composition solution coating is obtained through electrochemistry roughening and anodized using rotating coating
It is then 3 minutes dry in 145 DEG C of baking ovens on aluminum substrate, obtain 1.2 grams/m2Inner coating weight.Inner coating soaking is in isopropyl
It does not significantly dissolve or falls off within alcohol 1 minute, show its excellent anti-alcohol ability.
(2) external coating: 0.46 gram of PD-140A, 0.02 gram of IRD-85,0.01 gram of triazine D and 0.02 gram of crystal violet is molten
Solution is in the solvent mixture of 5.8 grams of propylene glycol monomethyl ethers and 3.8 grams of butanone-2s.Using rotating coating by the composition
It is then 3 minutes dry in 145 DEG C of baking ovens in solution coating to above-mentioned inner coating, obtain inner coating and external coating total weight
About 2.1 grams/m2Lighographic printing plate precursor (PP-2).
The Lighographic printing plate precursor (PP-2) that the present embodiment is prepared is in 800 Quantum-II type CTP system of Kodak
830nm laser is used on version machine, drum rotating speed 220rpm, laser power 12W are scanned exposure.Original after exposure
Version be diluted with water at 25 DEG C Konita DV-T developing liquid developing 35 seconds, obtained Lighographic printing plate precursor after development
The coating of exposed portion is all dissolved entirely, rather than the coating of exposed portion retains.Image clearly, clear-cut margin are neat.
Imageable element embodiment 3 prepares Lighographic printing plate precursor (PP-3)
(1) inner coating: 0.50 gram of polymeric binder PB-3,0.05 gram of PD494A and 0.01 gram of victoria blue BO are dissolved in
4.5 grams of glycol monoethyl ethers, 3.5 grams of butanone-2s, 1.0 grams of butyrolactone and 1.0 grams of water solvent mixture in.It is applied using rotation
Cloth method on the aluminum substrate obtained through electrochemistry roughening and anodized, then exists above-mentioned composition solution coating
It is 3 minutes dry in 145 DEG C of baking ovens, obtain 1.2 grams/m2Inner coating weight.Inner coating soaking is at isopropanol 1 minute without obvious
Dissolution or fall off, show its excellent anti-alcohol ability.
(2) external coating: by 0.46 gram of PD-140A, 0.02 gram of IRD-67,0.01 gram Irgacure 270 and 0.02 grams
Crystal violet is dissolved in the solvent mixture of 5.8 grams of propylene glycol monomethyl ethers and 3.8 grams of butanone-2s.It will using rotating coating
It is then 3 minutes dry in 145 DEG C of baking ovens in the composition solution coating to above-mentioned inner coating, obtain inner coating and outer painting
Layer total weight is about 2.1 grams/m2Lighographic printing plate precursor (PP-3).
The Lighographic printing plate precursor (PP-3) that the present embodiment is prepared is in 800 Quantum-II type CTP system of Kodak
830nm laser is used on version machine, drum rotating speed 220rpm, laser power 12W are scanned exposure.Original after exposure
Version is used Konita DV-T developing liquid developing 35 seconds at 25 DEG C, the exposed portion of obtained Lighographic printing plate precursor after development
Coating dissolution completely, rather than the coating of exposed portion retain.Image clearly, clear-cut margin are neat.
Imageable element embodiment 4 prepares Lighographic printing plate precursor (PP-4)
(1) inner coating: by 0.45 gram of polymeric binder PB-4,0.05 gram of methyl methacrylate and methacrylic acid copolymer
4.5 grams of glycol monoethyl ethers, 3.5 grams of butanone-2s, 1.0 grams of butyrolactone and 1.0 grams are dissolved in 0.01 gram of victoria blue BO
In the solvent mixture of water.Using rotating coating by above-mentioned composition solution coating through electrochemistry roughening and anodic oxidation
It handles on obtained aluminum substrate, it is then 3 minutes dry in 145 DEG C of baking ovens, obtain 1.2 grams/m2Inner coating weight.Inner coating
Soaking was not significantly dissolved or was fallen off at isopropanol 1 minute, showed its excellent anti-alcohol ability.
(2) 0.46 gram of EP-0090,0.02 gram of IRD-85 and 0.02 gram of crystal violet external coating: are dissolved in 5.8 gram third
In the solvent mixture of glycol monomethyl ether and 3.8 grams of butanone-2s.Using rotating coating by the composition solution coating to upper
It is then 3 minutes dry in 145 DEG C of baking ovens in the inner coating stated, it obtains inner coating and external coating total weight is about 2.1 grams/m2
Lighographic printing plate precursor (PP-4).
The Lighographic printing plate precursor (PP-4) that the present embodiment is prepared is in 800 Quantum-II type CTP system of Kodak
830nm laser is used on version machine, drum rotating speed 220rpm, laser power 12W are scanned exposure.Original after exposure
Version be diluted with water at 25 DEG C Konita DV-T developing liquid developing 35 seconds, obtained Lighographic printing plate precursor after development
The coating dissolution of exposed portion is complete, rather than the coating of exposed portion retains.Image clearly, clear-cut margin are neat.
Imageable element embodiment 5 prepares Lighographic printing plate precursor (PP-5)
(1) inner coating: 0.50 gram of polymeric binder PB-5,0.005 gram of IRD67 and 0.01 gram of victoria blue BO are dissolved in
4.5 grams of glycol monoethyl ethers, 3.5 grams of butanone-2s, 1.0 grams of butyrolactone and 1.0 grams of water solvent mixture in.It is applied using rotation
Cloth method on the aluminum substrate obtained through electrochemistry roughening and anodized, then exists above-mentioned composition solution coating
It is 3 minutes dry in 145 DEG C of baking ovens, obtain 1.2 grams/m2Inner coating weight.Inner coating soaking is at isopropanol 1 minute without obvious
Dissolution or fall off, show its excellent anti-alcohol ability.
(2) external coating: by 0.41 gram of PD-140A, 0.05 gram of SPN452,0.02 gram of IRD-85 and 0.02 gram of crystal violet
It is dissolved in the solvent mixture of 5.8 grams of propylene glycol monomethyl ethers and 3.8 grams of butanone-2s.Using rotating coating by the combination
It is then 3 minutes dry in 145 DEG C of baking ovens in object solution coating to above-mentioned inner coating, obtain inner coating and external coating gross weight
Amount is about 2.1 grams/m2Lighographic printing plate precursor (PP-5).
The Lighographic printing plate precursor (PP-5) that the present embodiment is prepared is in 800 Quantum-II type CTP system of Kodak
830nm laser is used on version machine, drum rotating speed 220rpm, laser power 12W are scanned exposure.Original after exposure
Version is developed 35 seconds at 25 DEG C with implementation after Konita DV-T developer solution and ethylene glycol ethyl ether mixing, obtained flat after development
The coating dissolution of the exposed portion of lithographic printing plate precursor is complete, rather than the coating of exposed portion retains.Image clearly, clear-cut margin
Neatly.
Imageable element embodiment 6 prepares Lighographic printing plate precursor (PP-6)
(1) 0.50 gram of polymeric binder PB-6 and 0.01 gram of victoria blue BO inner coating: are dissolved in 6.5 grams of ethylene glycol
Single ether, 2.0 grams of butanone-2s, 0.5 gram of butyrolactone and 0.5 gram of water solvent mixture in.It will be upper using rotating coating
It states composition solution to be coated on the aluminum substrate obtained through electrochemistry roughening and anodized, then in 145 DEG C of baking ovens
It is 3 minutes dry, obtain 1.2 grams/m2Inner coating weight.Inner coating soaking is at isopropanol 1 minute without significantly dissolving or taking off
It falls, shows its excellent anti-alcohol ability.
(2) 0.46 gram of EP0090G, 0.02 gram of IRD-85 and 0.02 gram of crystal violet external coating: are dissolved in 5.8 gram third
In the solvent mixture of glycol monomethyl ether and 3.8 grams of butanone-2s.Using rotating coating by the composition solution coating to upper
It is then 3 minutes dry in 145 DEG C of baking ovens in the inner coating stated, it obtains inner coating and external coating total weight is about 2.1 grams/m2
Lighographic printing plate precursor (PP-6).
The Lighographic printing plate precursor (PP-6) that the present embodiment is prepared is in 800 Quantum-II type CTP system of Kodak
830nm laser is used on version machine, drum rotating speed 220rpm, laser power 12W are scanned exposure.Original after exposure
Version is developed 35 seconds at 25 DEG C with implementation after Konita DV-T developer solution and ethylene glycol monomethyl ether mixing, obtained flat after development
The coating dissolution of the exposed portion of lithographic printing plate precursor is complete, rather than the coating of exposed portion retains.Image clearly, clear-cut margin
Neatly.
Imageable element embodiment 7 prepares Lighographic printing plate precursor (PP-7)
(1) 0.50 gram of polymeric binder PB-7 and 0.01 gram of victoria blue BO inner coating: are dissolved in 6.5 grams of ethylene glycol
Single ether, 2.0 grams of butanone-2s, 0.5 gram of butyrolactone and 0.5 gram of water solvent mixture in.It will be upper using rotating coating
It states composition solution to be coated on the aluminum substrate obtained through electrochemistry roughening and anodized, then in 145 DEG C of baking ovens
It is 3 minutes dry, obtain 1.2 grams/m2Inner coating weight.Inner coating soaking is at isopropanol 1 minute without significantly dissolving or taking off
It falls, shows its excellent anti-alcohol ability.
(2) external coating: by 0.46 gram of EP0090G, 0.02 gram of IRD-85,0.01 gram of WPI-170 and 0.02 gram of crystal violet
It is dissolved in the solvent mixture of 5.8 grams of propylene glycol monomethyl ethers and 3.8 grams of butanone-2s.Using rotating coating by the combination
It is then 3 minutes dry in 145 DEG C of baking ovens in object solution coating to above-mentioned inner coating, obtain inner coating and external coating gross weight
Amount is about 2.1 grams/m2Lighographic printing plate precursor (PP-7).
The Lighographic printing plate precursor (PP-7) that the present embodiment is prepared is in 800 Quantum-II type CTP system of Kodak
830nm laser is used on version machine, drum rotating speed 220rpm, laser power 12W are scanned exposure.Original after exposure
The Konita DV-T developer solution that version is diluted with water at 25 DEG C implements development 35 seconds, after development before obtained lithographic printing plate
The coating dissolution of the exposed portion of body is complete, rather than the coating of exposed portion retains.Image clearly, clear-cut margin are neat.
Imageable element embodiment 8 prepares Lighographic printing plate precursor (PP-8)
(1) inner coating: by 0.50 gram of polymeric binder PB-8,0.01 gram of WPI-170 and 0.01 gram of victoria blue R dissolution
In the solvent mixture of 6.5 grams of ethylene glycol monoethyl ethers, 2.0 grams of butanone-2s, 0.5 gram of butyrolactone and 0.5 gram of water.Utilize rotation
Turn coating method by above-mentioned composition solution coating on the aluminum substrate obtained through electrochemistry roughening and anodized, then
It is 3 minutes dry in 145 DEG C of baking ovens, obtain 1.2 grams/m2Inner coating weight.Inner coating soaking is not bright at isopropanol 1 minute
Aobvious dissolution falls off, and shows its excellent anti-alcohol ability.
(2) external coating: by 0.23 gram of PD140A, 0.23 gram of PD494A, 0.02 gram of IRD-67 and 0.02 gram of crystal violet
It is dissolved in the solvent mixture of 5.8 grams of propylene glycol monomethyl ethers and 3.8 grams of butanone-2s.Using rotating coating by the combination
It is then 3 minutes dry in 145 DEG C of baking ovens in object solution coating to above-mentioned inner coating, obtain inner coating and external coating gross weight
Amount is about 2.1 grams/m2Lighographic printing plate precursor (PP-8).
The Lighographic printing plate precursor (PP-8) that the present embodiment is prepared is in 800 Quantum-II type CTP system of Kodak
830nm laser is used on version machine, drum rotating speed 220rpm, laser power 12W are scanned exposure.Original after exposure
Version is used Konita DV-T developing liquid developing 35 seconds at 25 DEG C, the exposed portion of obtained Lighographic printing plate precursor after development
Coating dissolution completely, rather than the coating of exposed portion retain.Image clearly, clear-cut margin are neat.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (18)
1. a kind of positive-working lithographic printing plate precursor of sensitive for infrared radiation, it is characterised in that include:
(a) base,
(b) inner coating being covered on above base, the inner coating include a kind of repetition list derived from maleimide monomer
Member and the polymeric binder P for dissolving in alkaline-based developer, wherein other repetitive units except maleimide are derived from
Acidity coefficient pKaPolymerisable monomer greater than 8；
(c) external coating being covered on above inner coating, the external coating include a kind of infrared radiation absorption compound and are different from
Internally coated another kind polymeric binder Q.
2. the positive-working lithographic printing plate precursor of sensitive for infrared radiation according to claim 1, it is characterised in that: in described
The polymeric binder P that coating is included is indicated by following construction formula (I):
— (A) x—(B)y—(I)
Wherein A indicate derived from maleimide monomer () repetitive unit, B indicates derived from a kind of or more
Kind has ethylenically unsaturated groups and acidity coefficient pKaGreater than other repetitive units of 8 polymerisable monomers；And it is based on
The total weight of polymeric binder P, x account for 3-30 weight %, and y accounts for 70-93 weight %.
3. the positive-working lithographic printing plate precursor of sensitive for infrared radiation according to claim 1, it is characterised in that: described poly-
Closing the ratio between object adhesive P and inner coating total weight is 0.40:1 ~ 0.99:1.
4. the positive-working lithographic printing plate precursor of sensitive for infrared radiation according to claim 1, it is characterised in that: wherein institute
The inner coating stated also includes a kind of background contrast's dyestuff, and background contrast's dyestuff is in visible light region with high-selenium corn
Dyestuff, the additive amount of background contrast's dyestuff account for 0.1 ~ 8wt% of the inner coating total weight.
5. the positive-working lithographic printing plate precursor of sensitive for infrared radiation according to claim 4, it is characterised in that: the back
Scape comparative dye is one of oil-soluble dyes and/or basic dye or a variety of mixing.
6. the positive-working lithographic printing plate precursor of sensitive for infrared radiation according to claim 1, it is characterised in that: wherein institute
The inner coating stated also includes infrared radiation absorption compound, and the wavelength absorption range of the infrared radiation absorption compound is
700-1200nm, the additive amount of the infrared radiation absorption compound account for 0.1 ~ 8wt% of the inner coating total weight.
7. the positive-working lithographic printing plate precursor of sensitive for infrared radiation according to claim 6, it is characterised in that: described red
External radiation absorption compound be one of cyanine dye, anthraquinone dye, phthalocyanine dye, quinoneimine dye or methine cyanine dyes or
It is a variety of.
8. the positive-working lithographic printing plate precursor of sensitive for infrared radiation according to claim 1, it is characterised in that: wherein institute
The inner coating stated also includes acid agent, and the additive amount of the acid agent accounts for 0.1 ~ 10wt% of the inner coating total weight.
9. the positive-working lithographic printing plate precursor of sensitive for infrared radiation according to claim 8, it is characterised in that: the production
Sour agent is one of salt, triazine, acid anhydrides, diazonium naphthoquinone sulphonate or a variety of.
10. the positive-working lithographic printing plate precursor of sensitive for infrared radiation according to claim 1, it is characterised in that: described
Inner coating also includes polymeric binder P1, the polymeric binder P1 can be selected from phenolic resin, polystyrene derivative,
Polyurethane and different from one of polyacrylic acid (ester) of polymeric binder P or a variety of, the polymeric binder P1's
Additive amount accounts for 1 ~ 40wt% of the inner coating total weight.
11. the positive-working lithographic printing plate precursor of sensitive for infrared radiation according to claim 1, it is characterised in that: described
External coating include at least one infrared radiation absorption compound, the wavelength absorption range of the infrared radiation absorption compound exists
Between 700-1200nm, the additive amount of the infrared radiation absorption compound accounts for 0.5 ~ 10wt% of the external coating total weight.
12. the positive-working lithographic printing plate precursor of sensitive for infrared radiation according to claim 11, it is characterised in that: described
Infrared radiation absorption compound be cyanine dye, anthraquinone dye, phthalocyanine dye, quinoneimine dye or methine cyanine dyes one kind or
It is a variety of.
13. the positive-working lithographic printing plate precursor of sensitive for infrared radiation according to claim 1, it is characterised in that: described
External coating include a kind of polymeric binder Q, the polymeric binder Q can be derived from phenolic resin, poly- (hydroxy benzenes second
Alkene), one of polyurethane and polyacrylic acid (ester) or a variety of, the additive amount of the polymeric binder Q accounts for the external coating
80 ~ 99.5wt% of total weight.
14. the positive-working lithographic printing plate precursor of sensitive for infrared radiation according to claim 1, it is characterised in that: described
External coating also includes dissolution inhibitor, and the dissolution inhibitor is in triarylmethane dye, salt, ketone or ester type compound
One or more, the additive amount of the dissolution inhibitor accounts for 0.1 ~ 20wt% of the external coating total weight.
15. the positive-working lithographic printing plate precursor of sensitive for infrared radiation according to claim 1, it is characterised in that: described
External coating may also contain a kind of acid agent, the acid agent can be selected from salt, triazine, acid anhydrides, diazonium naphthoquinone sulphonate one
Kind is a variety of, and the additive amount of the acid agent accounts for 0.2 ~ 10wt% of the inner coating total weight.
16. the positive-working lithographic printing plate precursor of sensitive for infrared radiation according to claim 1, which is characterized in that described
Base is the aluminium base through electrolysis roughening and anodized.
17. the side that a kind of positive-working lithographic printing plate precursor of -16 sensitive for infrared radiation according to claim 1 forms image
Method, it is characterised in that: the described method includes: A) it is real with infra-red radiation Lighographic printing plate precursor described in claim 1-16
Apply by image exposure, to form the image-forming component containing exposure and unexposed area, B) make the image-forming component and alkalinity
Developer contact is only to remove the exposure area, manufactured lithographic printing plate.
18. according to the method for claim 17, it is characterised in that: wherein described to use wavelength 700- by image exposure
The infrared laser of 1200 nm radiation carries out, and the alkaline developer is aqueous solution of the pH value less than 14.
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| CN201910086321.0A CN110007564B (en) | 2019-01-29 | 2019-01-29 | Multi-coat infrared radiation sensitive positive working lithographic printing plate precursor and method of forming image |
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| CN111123646A (en) * | 2020-01-14 | 2020-05-08 | 浙江康尔达新材料股份有限公司 | Ultraviolet and visible light sensitive positive-working imageable element and method of forming images therewith |
| CN111158214A (en) * | 2019-12-31 | 2020-05-15 | 浙江康尔达新材料股份有限公司 | Infrared radiation sensitive positive-working imageable element and method of forming image therewith |
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| WO2021136558A1 (en) * | 2019-12-31 | 2021-07-08 | 浙江康尔达新材料股份有限公司 | Infrared radiation sensitive positive-working imageable element and method for forming image using same |
| CN111123646A (en) * | 2020-01-14 | 2020-05-08 | 浙江康尔达新材料股份有限公司 | Ultraviolet and visible light sensitive positive-working imageable element and method of forming images therewith |
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| CN110007564B (en) | 2022-05-20 |
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