CN1987647A - Thermosensitive polymerized lithographic printing plate - Google Patents
Thermosensitive polymerized lithographic printing plate Download PDFInfo
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- CN1987647A CN1987647A CN 200510107307 CN200510107307A CN1987647A CN 1987647 A CN1987647 A CN 1987647A CN 200510107307 CN200510107307 CN 200510107307 CN 200510107307 A CN200510107307 A CN 200510107307A CN 1987647 A CN1987647 A CN 1987647A
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Abstract
The planographic plate includes supporter and thermal polymerization layer. The thermal polymerization layer includes polymerisable functional macromolecule binding agent of unsaturated base group of ethene possessing structure i and ii. Containing copolymers in three types of construction unit, the thermolabile planographic plate possesses advantages: strong adhesion, tough coat layer, good solubility, better coating performance, as well as durable printing operability, larger development latitude etc. Presswork with fine image is obtained by using UV printing ink.
Description
Technical field
The present invention relates to contain in a kind of functional polymer and the thermal polymerization layer sense infrared laser lithographic plate of this functional polymer, more detailed saying, relate to a kind of polyvinyl and have the photosensitive compounds that acts on negative type, the photographic layer ink affinity is good, photographic layer and base adhesion are big, the characteristics that the imaging layer pressrun is high, and the photographic layer chemical resistance is good, is suitable for the UV ink printing.Specifically relate to a kind of thermosensitive polymerized lithographic printing plate.
Background technology
As the printing plate of laser scanning exposure direct imaging, the structure that can buy on market comprises a hydrophilic carrier and a lipophilicity sensible heat resin bed disposed thereon, that can produce the active substance of free radical or Shandong this acid of clothing and so on by laser radiation.Negative type or positive-working lithographic printing plate can obtain like this.Specifically; the negative type printing heat-sensitive lithographic printing planography comprises the imaging layer of a hydrophilic carrier and a sense infrared laser disposed thereon; the imaging layer of this sense infrared laser has the infrared absorbent of energy absorbing IR ray; there is heat absorption to produce the initiating agent of thermal polymerization; a kind of alefinically unsaturated compounds that can carry out addition polymerization; a kind of polymer adhesive that can be dissolved in the alkaline developer, and a kind of oxygen shielding protection layer that can be provided with as required.This negative type printing heat-sensitive lithographic printing planography has some good performances, as high resolving power, high press resistance rate, process simple etc., thereby make it become the possibility of desirable printing plate.
United States Patent (USP) NO.4123276 have disclosed functional acrylic resin, and its acid number is between 10-100, and its composition is (methyl) acrylic acid, (methyl) acrylic acid hydroxy alkyl ester, and propylene cyanogen.Day disclosure special permission NO.SHO57-51656 has disclosed functional acrylic resin and has also comprised the aromaticity hydroxyl compound, forms as the unit of 2-hydroxyl-3 phenoxy group (methyl) propyl acrylate.Day disclosure special permission NO.SHO61-285449 and NO.HEI 10-282658 has disclosed the functional acrylic resin that unsaturated group is arranged on the side chain.
US2002/0142249 has disclosed with polyvinyl alcohol (PVA) and has carried out modification, makes it connect polymerisable functional groups, has the acidic-group of available bases water development simultaneously.The light sensitive layer of the grateful light that this resin is formed promptly can be used as the photosensitive coating of grateful light, also can be used as the temperature-sensitive coating of grateful light
European patent document EP617997 discloses the functional acrylic resin that contains mean molecular weight 150000 in its floating coat, pentaerythritol triacrylate, triazines and quarternary ammonium salt compound, the forme that the IR dyestuff makes, but do not have the acid number of maniflest function based acrylic resin to form with concrete.
The technician studies the various high molecular polymers as film forming matter, but have following defective such as above-mentioned functional acrylic resin: the cohesive to the version base is bad, and coating is bad, wears no resistance, poor storage stability, the seal journey when especially using UV printing ink is lower.
Summary of the invention
Purpose of the present invention just is to provide at the problems referred to above a kind of thermosensitive polymerized lithographic printing plate of better effects if.
The present invention includes support and thermal polymerization layer, wherein the thermal polymerization layer includes the polymerisable functional high-polymer bonding agent of the ethene unsaturated group with structure i and ii (A); Functional high-polymer adhesive construction with structure i and ii is as follows:
I has following two kinds of structures (a), and (b) unit is one of any:
(a) has alkali-soluble structural unit
In the formula X1 represent-O-or-NR3-, R1 represents-H or-CH3, what R2 represented singly-bound or divalent has a switch base, Y1 represents arylene, n represents 0 or 1, R3 represents to have alkyl, naphthenic base, the aryl or aralkyl of a hydrogen atom or a substituent 1-12 carbon atom; Z1 represents to have the group of acid hydrogen atom, and m represents the integer more than 1;
(b) has the structural unit of alkali-soluble maleimide
Z represents to have the group of acid hydrogen atom, can be-COOH ,-OH or-SO2NH2;
Ii has the carboxylic acid esters structure that acid causes phase transition property:
R represents alkyl, naphthenic base, aralkyl.
The thermal polymerization layer contains the polymerisable functional high-polymer bonding agent of the ethene unsaturated group with structure i and ii (A) among the present invention, also contain: unsaturated free radical polymerization monomer and oligomer (B), can absorbing IR the infrared absorbent (C) of ray, can produce at least a thermal polymerization (D) of free radical.
Containing the quality of compound unit in high molecular polymer that has the alkali solubility group shown in (a) among the present invention is 0-60% than content, be preferably 10-30%, containing the quality of compound unit in high molecular polymer that has the alkali solubility group shown in (b) is 0-60% than content, be preferably 10-30%, containing the quality of the compound unit shown in (c) in high molecular polymer is 1-50% than content, is preferably 10-25%.
Thermosensitive polymerized lithographic printing plate according to claim 1 and 2 among the present invention, it is characterized in that: the weight average molecular weight of described polyvinyl is more than 3000, be preferably 5000-20 ten thousand, number-average molecular weight is at 1500 above high molecular polymers, be preferably 3000-20 ten thousand, dispersion degree is greater than 1.4.
The polyvinyl total acid number is 70mg KOH/g or lower among the present invention.
Can absorbing IR among the present invention the infrared absorbent (C) of ray, the infrared absorbent of this IR ray contains a kind of of dyestuff that the absorption maximum scope is 760-1200nm and pigment.
The infrared absorbent (C) of energy absorbing IR ray is among the present invention
Wherein each X can be S, O, NR or C (alkyl) 2 independently;
Each R
1Can be alkyl, alkyl azochlorosulfonate or alkyl ammonium group independently;
R
2Can be hydrogen, halogen, SR, SO
2R, OR or NR
2
Each R
3Can be hydrogen, alkyl, COOR, OR, SR, SO independently
3 -, NR
2, halogen and the fused benzo ring that not necessarily replaces;
A
-The expression negative ion;
---expression nonessential five yuan or six-membered carbon ring;
Wherein each R can be hydrogen, alkyl and aryl independently; With
Wherein each n can be 0,1,2 or 3 independently.
Thermal polymerization among the present invention (D) preferably comprises compound in triazine class.
Thermosensitive polymerized lithographic printing plate also comprises and is selected from iodine salt, diazo salt and sulphur salt as thermal polymerization (D) among the present invention.
Advantage of the present invention is as follows: contain in the sensible heat flat stamping version have above-mentioned (a) and (b), (c) expression structural unit multipolymer, make that thus flat stamping version of the present invention has strong adhesion, coating is tough and tensile; The superpolymer dissolubility is good, so the coating in when coating is good on support.Flat stamping version of the present invention has that good printing-force-resistence, development tolerance are big, alkali resistant membrane left rate height, solvent resistance are strong.Can get the printed matter of image fineness when using the UV ink printing.
Embodiment:
The present invention does with detailed explanation below in conjunction with embodiment:
Embodiment 1,
The present invention includes support and thermal polymerization layer, wherein the thermal polymerization layer includes the polymerisable functional high-polymer bonding agent of the ethene unsaturated group with structure i and ii (A); Functional high-polymer adhesive construction with structure i and ii is as follows:
I has following two kinds of structures (a), and (b) unit is one of any:
(a) has alkali-soluble structural unit
In the formula X1 represent-O-or-NR3-, R1 represents-H or-CH3, what R2 represented singly-bound or divalent has a switch base, Y1 represents arylene, n represents 0 or 1, R3 represents to have alkyl, naphthenic base, the aryl or aralkyl of a hydrogen atom or a substituent 1-12 carbon atom; Z1 represents to have the group of acid hydrogen atom, and m represents the integer more than 1;
(b) has the structural unit of alkali-soluble maleimide
Z represents to have the group of acid hydrogen atom.As-COOH ,-OH ,-SO2NH2 etc.;
Ii has the carboxylic acid esters structure that acid causes phase transition property:
R represents alkyl, naphthenic base, aralkyl.
The thermal polymerization layer contains the polymerisable functional high-polymer bonding agent of the ethene unsaturated group with structure i and ii (A) among the present invention, also contain: unsaturated free radical polymerization monomer and oligomer (B), can absorbing IR the infrared absorbent (C) of ray, can produce at least a thermal polymerization (D) of free radical.
Containing the quality of compound unit in high molecular polymer that has the alkali solubility group shown in (a) among the present invention is 0-60% than content, is preferably 10-30%, specifically can adopt 0% or 10% or 20% or 30% or 40% or 50% or 60% etc.; Containing the quality of compound unit in high molecular polymer that has the alkali solubility group shown in (b) is 0-60% than content, is preferably 10-30%, 0% or 10% or 20% or 30% or 40% or 50% or 60% etc.; Containing the quality of the compound unit shown in (c) in high molecular polymer is 1-50% than content, is preferably 10-25%.1% or 10% or 20% or 25% or 30% or 40% or 50% etc.;
Thermosensitive polymerized lithographic printing plate according to claim 1 and 2 among the present invention, it is characterized in that: the weight average molecular weight of described polyvinyl is more than 3000, be preferably 5000-20 ten thousand, specifically can adopt 5000 or 10,000 or 20,000 or 50,000 or 100,000 or 150,000 or 200,000 etc., number-average molecular weight is at 1500 above high molecular polymers, be preferably 3000-20 ten thousand, specifically can adopt 1500 or 2000 or 3000 or 5000 or 10,000 or 20,000 or 50,000 or 100,000 or 150,000 or 200,000 etc., dispersion degree is greater than 1.4.
The polyvinyl total acid number is 70mg KOH/g or lower among the present invention.
The infrared absorbent (C) of energy absorbing IR ray among the present invention, the infrared absorbent of this IR ray contains a kind of of dyestuff that the absorption maximum scope is 760-1200nm and pigment, specifically can adopt 760nm or 800nm or 900nm or 1000nm or 1100nm or 1200nm etc.
The infrared absorbent (C) of energy absorbing IR ray is among the present invention
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, SO
2R, OR or NR
2
Each R
3Can be hydrogen, alkyl, COOR, OR, SR, SO independently
3 -, NR
2, halogen and the fused benzo ring that not necessarily replaces;
A
-The expression negative ion;
---expression nonessential five yuan or six-membered carbon ring;
Wherein each R can be hydrogen, alkyl and aryl independently; With
Wherein each n can be 0,1,2 or 3 independently.
Thermal polymerization among the present invention (D) preferably comprises compound in triazine class.
Thermosensitive polymerized lithographic printing plate also comprises and is selected from iodine salt, diazo salt and sulphur salt as thermal polymerization (D) among the present invention.
Embodiment 2,
The present invention includes: support and thermal polymerization layer, wherein the thermal polymerization layer contains the polymerisable functional high-polymer bonding agent of the ethene unsaturated group with structure i and ii (A).Also contain unsaturated free radical polymerization monomer and oligomer (B), can absorbing IR the infrared absorbent (C) of ray, can produce at least a compound (D) of free radical.
Functional high-polymer bonding agent (A)
The structure that functional high-polymer bonding agent (A) has structure i and ii is as follows:
I has following two kinds of structural units:
(a) has alkali-soluble structural unit
In the formula X1 represent-O-or-NR3-, R1 represents-H or-CH3, what R2 represented singly-bound or divalent has a switch base, Y1 represents arylene, n represents 0 or 1, R3 represents to have alkyl, naphthenic base, the aryl or aralkyl of a hydrogen atom or a substituent 1-12 carbon atom.Z1 represents to have the group of acid hydrogen atom, and m represents the integer more than 1;
(b) has the structural unit of alkali-soluble maleimide
Z represents to have the group of acid hydrogen atom.As-COOH ,-OH ,-SO2NH2 etc.;
Ii has the carboxylic acid esters structure that acid causes phase transition property:
R represents alkyl, naphthenic base, aralkyl.
The functional high-polymer that uses in the lithographic plate of sensible heat laser imaging of the present invention (A) contains the ethene unsaturated group with structure i and ii.Purpose of the present invention is exactly the advantage of while in conjunction with two kinds of groups, promptly containing the monomer of sulfonamides group, the monomer copolymerization of phenolic hydroxy group class, superpolymer contains N substituted acrylamide class formation and maleimide class formation simultaneously, and connect functional pair of key by graft reaction, and control macromolecule iodine number, by the acid number size of control polymeric acidic group, make plate have simultaneously that alkali resistance is good, the development tolerance big, the wearing quality drug resistance is all very good, the storage stability height.
Specifically, utilize the photographic layer of the functional high-polymer of the monomer contain the sulfonamides group and N substituted acrylamide class formation to realize the present invention exactly as the flat stamping version.Polyvinyl contains the multipolymer of following (a) and (b), (c) three kinds of structural units:
Structural unit (a) with alkali solubility group
In the formula, X1 represents-O-or-NR3-, R1 represents-H or-CH3, R2 represents the organic group of singly-bound or divalent, Y1 represents arylene, Z1 represents-OH ,-COOH ,-SO2NHR4 ,-NHSO2R5, CONHSO2R6 ,-SO2NHCOR7 ,-NHCONHSO2R3 ,-SO2NHCONHR9 ,-CONHSO2NHR10, NHSO2NHCOR11 ,-SO2NHSO2R12 ,-COCH2COR13 ,-OCONHSO2R14, SO2NHCOOR15.N represents 0 or 1, and when R2 is singly-bound and Z1 during for-OH, n is 1, and m represents the integer more than 1.R3 represents to have alkyl, naphthenic base, the aryl or aralkyl of a hydrogen atom or a substituent 1-12 carbon atom.R4, R9, R10 represent to have alkyl, naphthenic base, fragrance or the aralkyl of a hydrogen atom or a substituent 1-12 carbon atom.R5, R6, R7, R8, R11, R12, R13, R14, R15 represent to have alkyl, naphthenic base, the aryl or aralkyl of substituent 1-12 carbon atom.
Structural unit with alkali-soluble maleimide
Z represents-OH ,-COOH ,-SO2NHR4 ,-NHSO2R5, CONHSO2R6 ,-SO2NHCOR7 ,-NHCONHSO2R3 ,-SO2NHCONHR9 ,-CONHSO2NHR10, NHSO2NHCOR11 ,-SO2NHSO2R12 ,-COCH2COR13 ,-OCONHSO2R14, SO2NHCOOR15.R4, R9, R10 represent to have alkyl, naphthenic base, fragrance or the aralkyl of a hydrogen atom or a substituent 1-12 carbon atom.R5, R6, R7, R8, R11, R12, R13, R14, R15 represent to have alkyl, naphthenic base, the aryl or aralkyl of substituent 1-12 carbon atom.)
Has the carboxylic acid esters structure that acid causes phase transition property
R represents alkyl, naphthenic base, aralkyl.
The optional usefulness of superpolymer that the present invention uses has the structural unit of structure i and ii.Functional high-polymer resin among the present invention is as a crosslinkable bonding agent, except the structural unit that contains structure i and ii, preferably contains the multipolymer of the polymerizable compound of more than one other different with (a) and (b), (c) structure.With (a) and (b), polymerizable compound that (c) structure is different is the compound that screens from acrylic compounds, esters of acrylic acid, phenylethylene, vinyl cyanide.
Esters of acrylic acid: as methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, methacrylic acid pentyl ester, α-Jia Jibingxisuan-beta-hydroxy ethyl ester, methyl acrylate, ethyl acrylate, butyl acrylate, acrylic acid pentyl ester, epihydric alcohol methylpropenoic acid ester, pentaerythrite monomethacrylates or the like.
Phenylethylene: methyl styrene, styrene, 4-hydroxy styrenes or the like.
Acrylic compounds: methacrylic acid, acrylic acid or the like.
Vinyl cyanide: vinyl cyanide, methacrylonitrile or the like.
Preferred monomers is in the above monomer: methacrylic acid, acrylic acid, methyl methacrylate, styrene, acrylic acid pentyl ester, vinyl cyanide, methacrylonitrile or the like.
Functional high-polymer resin among the present invention except the structural unit that contains structure i and ii, in order to improve the figure layer intensity of image area, also should have bridging property on its main chain of binder polymer or the side chain as a crosslinkable bonding agent.In order to give the binder polymer bridging property, can on the trunk of polymkeric substance or side chain, introduce crosslinkable functionality, as alkene formula unsaturated link.By copolymerization or by the polymer graft reaction, can introduce crosslinkable functionality, as the acryloyl key, methacryl key, allyl base key etc.
The polymerisable lithographic plate of sensible heat, the functional polymer total acid number that it is characterized in that containing vinyl is 70mg KOH/g or lower.The functional polymer total acid number is too high, subtracts film easily with solidifying image after the laser imaging; The functional polymer total acid number is the end too, solidifies image after the imaging and is not easy to develop, and picture resolution is too poor.
The preferred content of the crosslinkable groups in binder polymer (but the content of the unsaturated double-bond of free crowd, by the iodometric titration decision) be 0.1 to 10.0 mM/every gram binder polymer, more preferably 1.0 to 7.0 mMs/every gram binder polymer most preferably is 2.0 to 5.5 mMs/every gram binder polymer.In this scope, the storage stability that the susceptibility of image recording layer and image recording layer form coating solution is good especially.
This high molecular polymer, (a) quality of compound unit in high molecular polymer that has the alkali solubility group shown in is 1-60% than content, be preferably 10-30%, containing the quality of compound unit in high molecular polymer that has the alkali solubility group shown in (b) is 1-60% than content, be preferably 10-30%, containing the quality of the compound unit shown in (c) in high molecular polymer is 1-50% than content, is preferably 10-25%.
The preferred adhesive polymkeric substance is characterized in that the weight average molecular weight of polyvinyl more than 3000, is preferably 5000-20 ten thousand, and number-average molecular weight is preferably 3000-20 ten thousand at 1500 above high molecular polymers, and dispersion degree is greater than 1.4.
But in sensible heat laser imaging flat stamping version of the present invention, contain have above-mentioned (a) and (b), (c) expression structural unit multipolymer, make that thus flat stamping version of the present invention has strong adhesion, coating is tough and tensile, the superpolymer dissolubility is good, so the coating in when coating is good on support.Flat stamping version of the present invention has good printing-force-resistence, the development tolerance is big, solvent resistance is strong advantage, can get the printed matter of image fineness when using the UV ink printing.
Can be by known method composite adhesives polymkeric substance.Particularly, by free radical polymerization or polyreaction, can easily synthesize the binder polymer that in side chain, has crosslinkable groups.Operable radical polymerization initiator comprises in the free radical polymerization: compound known such as azo initiator and peroxide initiator.
Operable examples of solvents comprises tetrahydrofuran, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methyl alcohol, ethanol, glycol monoethyl ether, ethylene glycol monoethyl ether, acetate 2 one methoxyl ethyl esters, diethylene glycol dimethyl ether, fore-telling methoxyl one 2 monopropylene glycols, acetate 1 one methoxyls one 2 one propyl ester, N in building-up process, N dimethyl formamide, N, N one dimethyl acetamide, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide and water.Can use these separately or use its two or more potpourri.Polymerisable monomer and oligomer (B)
But the photosensitive layer that is used for the negative flat stamping version of thermal polymerization, but and the polyaddition compounds that has at least one ethylenical unsaturated double bonds be selected from and have at least one, preferably have a compound of two or more terminal ethylenic unsaturated bonds.Known these compounds can be used to need not among the present invention any particular restriction in relevant industrial circle.These compounds can have such as monomer, prepolymer (being dipolymer, trimer and oligomer), their potpourri and the chemical species of multipolymer.The example of monomer and multipolymer thereof comprises: the ester and the acid amides of unsaturated carboxylic acid (for example acrylic acid, methacrylic acid, itaconic acid, crotonic acid, iso-crotonic acid or maleic acid), this carboxylic acid, wherein preferred compound is the acid amides of ester, unsaturated carboxylic acid and the aliphatic polyamine compound of unsaturated carboxylic acid and aliphatic polyol.What can preferably use equally is: have the ester of unsaturated carboxylic acid of nucleophilic displacement of fluorine base (as hydroxyl, amino or sulfydryl) or the addition compound product of acid amides and simple function or polyfunctional isocyanates or epoxide, or have the ester of unsaturated carboxylic acid of nucleophilic displacement of fluorine base (as hydroxyl, amino or sulfydryl) or the dehydration condensation product of acid amides and simple function or polyfunctional carboxylic acids.In addition, also preferably use, or carry out the resulting product of substitution reaction with the ester of unsaturated carboxylic acid or acid amides and simple function or polyfunctional alcohol, amine or thiol by the ester of the unsaturated carboxylic acid that has close electric substituting group (as isocyanate group or epoxy radicals) or the resulting product of addition reaction between acid amides and simple function or polyfunctional alcohol, amine or the thiol.As other example, also can use unsaturated carboxylic acid is replaced with the resulting product of similar reaction behind unsaturated phosphonic acids, styrene or the vinyl ether.
The instantiation of monomer of form that is the ester of aliphatic polyol and unsaturated carboxylic acid comprises: acrylate, as ethylene glycol diacrylate, the diacrylate triglycol ester, diacrylate-1,3 one butanediol esters, diacrylate 1,4. butanediol ester, the diacrylate propylene glycol ester, diacrylic acid pentyl diol ester, trimethylolpropane triacrylate, trimethylolpropane tris (acryloyl-oxy propyl group) ether, the trimethylolethane trimethacrylate acrylate, hexanediol diacrylate, diacrylate-1,4 cyclohexanediol esters, diacrylate TEG ester, the diacrylate pentaerythritol ester, pentaerythritol triacrylate, pentaerythritol tetracrylate, the diacrylate dipentaerythritol ester, six acrylic acid dipentaerythritol ester, three acrylic acid sorbitol esters, tetrapropylene acid sorbitol ester, five acrylic acid sorbitol esters, six acrylic acid sorbitol esters, three (acrylyl oxy-ethyl) isocyanates and polyester acrylic ester oligomer: methacrylate, as dimethacrylate 1, the 4-butanediol ester, the dimethacrylate triglycol ester, the dimethacrylate DOPCP, trimethylol-propane trimethacrylate, the trimethylolethane trimethacrylate methacrylate, Ethylene glycol dimethacrylate, dimethacrylate-1, the 3-butanediol ester, dimethacrylate hexanediol ester, the dimethacrylate pentaerythritol ester, trimethyl acrylic acid pentaerythritol ester, pentaerythritol tetramethacrylate, the dimethacrylate dipentaerythritol ester, hexamethyl acrylic acid dipentaerythritol ester, trimethyl acrylic acid sorbitol ester, tetramethyl acrylic acid sorbitol ester, two [right-(3-formyloxy-2-hydroxyl propoxyl group) phenyl] dimethylmethanes and two [right-(formyloxy ethoxy) phenyl] dimethylmethane; Itaconate is as two itaconic acid glycol esters, two itaconic acid propylene glycol esters, two itaconic acids-1,3 butylene glycol ester, two itaconic acid 1-4-butanediol esters, two itaconic acid 1-4-butanediol esters, two itaconic acid pentaerythritol esters and four itaconic acid sorbitol esters; Crotonates, as two crotonic acid glycol esters, two crotonic acids-1,4-butanediol ester, two crotonic acid pentaerythritol esters and four crotonic acid sorbitol esters: iso-crotonic acid ester, as two iso-crotonic acid glycol esters, two iso-crotonic acid pentaerythritol esters and four iso-crotonic acid sorbitol esters; Maleate is as two maleic acid glycol esters, two maleic acid triglycol esters, two maleic acid pentaerythritol esters and four maleic acid sorbitol esters; And other esters, those described in Japanese Patent Application Publication 5240/1984,5241/1984 and 226149/1990 have the ester of aromatic backbone structure;
And described in the Japanese Patent Application Publication 165613/1989 those contain amino ester.These all esters all can be preferably with in the present invention.
The ester monomer of enumerating previously can use with the form of its potpourri.
Infrared absorbent (C)
Useful infrared absorbing compounds typically has maximum absorption wavelength in certain a part of electromagnetic spectrum greater than about 750nm; More particularly, their maximum absorption wavelength scope is 780-1100nm.
Preferred ingredient (a) comprises at least a compound that is selected from triarylamine dyestuff, thiazole dyestuff, indoles dyestuff, oxazole dyestuff, cyanine dyes, polyaniline dye, polypyrole dye, polythiophene dye, leuco dye and phthalocyanine color and the dyestuff.
More preferably component 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, SO
2R, OR or NR
2
Each R
3Can be hydrogen, alkyl, COOR, OR, SR, SO independently
3 -, NR
2, halogen and the fused benzo ring that not necessarily replaces;
A
-The expression negative ion;
---expression nonessential five yuan or six-membered carbon ring;
Wherein each R can be hydrogen, alkyl and aryl independently; With
Wherein each n can be 0,1,2 or 3 independently.
If R
1Be alkyl azochlorosulfonate, then owing to having formed inner salt, so A
-Can not exist and alkali metal cation will be essential as gegenion.If R
1Be alkyl ammonium group, then will need second kind of negative ion as gegenion.Second kind of negative ion can with A
-Identical maybe can be different negative ion.
Preferred IR absorbing agent (a) is with the about 20wt% of about 0.05wt%-, preferably about 0.5-8wt% and more preferably from about the consumption of 1.0-3wt% be present in the IR sensing composition, based on the total solids content of IR sensing composition.
Radical initiator (D)
Another key component of initiator system is the compound (D) that can produce free radical.Heat decomposable radical-forming agent is meant the compound that uses and produce free radical with above-mentioned IR absorbing agent with the IR laser radiation time.This radical-forming agent comprises: salt, the triaizine compounds that contains trihalomethyl group, superoxide, azo class polymerization initiator, triazo-compound and quinone two nitrine, in them, the triaizine compounds of trihalomethyl group and salt become preferably because of its hypersensitivity.Particularly preferably be the compound that multi-haloalkyl replaces.These are to contain halogenation more than or the substituent compound of several single halogenated alkyls.Halogenated alkyl preferably has 1-3 carbon atom.Preferred especially halogenation methyl.
The absorptive character of the compound that multi-haloalkyl replaces have determined the sunlight stability of IR sensing composition basically.The compound that UV/VIS absorbs maximal value＞330nm causes keeping 6-8 minute under daylight at forme, and then after the heating, the composition that may develop no longer fully.The not only available IR of this composition, and available UV radiation becomes the exposure of image ground.If wish the sunlight stability of higher degree, the compound that then preferred multi-haloalkyl replaces, this compound＞330nm place does not have UV/VIS absorption maximal value.
Thermal polymerization inhibitor
But in negative type photosensitive layer as the thermal polymerization of particularly preferred embodiment of the present invention, preferably added the small amount of thermal polymerization inhibitor and to prevent the compound that has ethylenical unsaturated double bonds undesirable thermal polymerization has taken place, this thermal polymerization may occur in the production or the memory period of negative type photosensitive composition.Suitable thermal polymerization inhibitor comprises: quinhydrones, p methoxy phenol, BHT, 1,2,3,-thrihydroxy-benzene, tert-butyl catechol, benzoquinones, 4,4 '-thiobis-(3 methy 6 tert butyl phenol), 2,2 '-di-2-ethylhexylphosphine oxide (4-methyl isophthalic acid 6-tert-butyl phenol), and uncle's cerium salt of N-nitroso-phenyl hydramine.The interpolation of thermal polymerization inhibitor
25 amounts preferably account for about 0.01 ‰ about 5% (weight) of nonvolatile component in the composition.
Can mix colorant such as dyestuff or pigment in the photosensitive layer of photosensitive planographic plate of the present invention to carry out painted to it.Adopt this measure, but the detectability of said galley be improved, show as and after plate-making, be easy to galley is carried out visual inspection or shown as adaptability to the image density measuring equipment.Because most of dyestuffs can reduce the photographic speed of photopolymerization photosensitive layer, thereby preferably use pigment as colorant.Specifically, can use the pigment such as phthalocyanine and AZO pigments, carbon black and titanium dioxide, and the dyestuff such as ethyl violet, crystal violet, azo dyes, anthraquinone dye and cyanine dye.The consumption of these dyestuffs or pigment preferably accounts for about 0.5 ‰ about 5% (weight) of nonvolatile component in the composition.
In order further to improve the physical property of cross-linked layer, can mix known various adjuvants in this technical field, comprise inorganic filler, plastifier and can strengthen the oleophylic agent of the absorbency on photosensitive layer surface.
In order to make photosensitive layer, the photopolymer compositions that is used to form this layer can be dissolved in the various organic solvents, and the coating mixture of gained is coated on the carrier by applying.The solvent that is used for this purpose comprises: acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, glycol monomethyl ether, ethylene glycol monoethyl ether, glycol dimethyl ether, the propylene glycol monomethyl ether, propylene glycol monoethyl ether, diacetone, cyclohexanone, diacetone alcohol, methyl glycol acetate, ethyl cellosolve acetate, ethylene glycol one isopropyl ether, butyl cellosolve acetate, the 3-methoxypropanol, methoxymethoxy ethanol, methyl carbitol, diethylene glycol one ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetic acid esters, ethoxy propyl acetate, acetate .3-methoxyl propyl ester, the N.N-dimethyl formamide, dimethyl sulfoxide, bifurcation-butyrolactone, methyl lactate, and ethyl lactate.Solvent can use with pure material form or form of mixtures.The solid content of coating mixture is generally 2-50% (weight).
But as the carrier of the negative type heat-sensitive layer of the present invention's thermal polymerization, can not be subjected to any restrictedly use in this technical field known, and any hydrophilic carrier that has been used to printing heat-sensitive lithographic printing planography.The form of this carrier is large scale and stable plate preferably, preferred concrete material for example comprises: paper, with the compound paper of plastics (as tygon, polypropylene or polystyrene), sheet metal (as aluminium, zinc or copper), plastic sheeting (as cellulose diacetate, cellulose triacetate, cellulose propionate, acid fiber element, acetate acid fiber element, cellulose nitrate, poly-(ethylene glycol terephthalate), tygon, polystyrene, polypropylene, polycarbonate or Pioloform, polyvinyl acetal), and compound or gas deposition the paper or the plastic sheeting of above-mentioned metal.In order to give water wettability or to strengthen surface strength, if desired and necessary, can carry out suitable physics or chemical surface treatment well known in the art to this carrier.
Particularly preferred carrier comprises paper, mylar and aluminium sheet.In them, aluminium sheet is more preferred, because the dimensionally stable of aluminium is relatively more cheap, and the surface with a water wettability and mechanical property excellence.It also is preferred comprising the composite plate that is attached to the aluminium sheet on poly-(ethylene glycol terephthalate) film.
But in lithographic plate, it is desirable to a protective seam is set on above-mentioned heat sensing layer so that in air, carry out image exposure with thermal polymerization photosensitive layer as the preferred embodiment of the invention.This protective seam can prevent the oxygen that exists in the air or pollute photosensitive layer such as the low molecular weight compound (the two all can hinder the imaging reaction that is caused by to above-mentioned photosensitive layer exposure) of alkaline matter, thereby the temperature-sensitive plate can be exposed in the air.Therefore, wish that the performance that this protective seam has comprises: the first, have low low-molecular-weight molecule (as oxygen) perviousness, in addition, have easy removal in the developing process behind image exposure.Various suggestions have been proposed protective seam, as at US 3,458,3111 and Japanese Patent Application Publication 49729/1980 in elaborate.
As the material that is used for protective seam, preferably has the water-soluble polymers of higher crystallinity.Water-soluble polymers is specifically arranged, as poly-(vinyl alcohol), polyvinylpyrrolidone, acid cellulose derivant, gelatin, gum arabic and poly-(allyl phenol.Use poly-(vinyl alcohol) can obtain best key property, as refuse the removeability during oxygen and the development as the principal ingredient of protective seam.Poly-(vinyl alcohol) that be used in the protective seam can partly be replaced by ester, ether or acetal, as long as remaining capacity unsubstituted poly-(vinyl alcohol) is repelled degree and water-soluble to guarantee necessary oxygen.Equally, poly-(vinyl alcohol) can partly contain the composition of other copolymerization.The monomeric unit that the instantiation of poly-(vinyl alcohol) includes 71-100% has been hydrolyzed and molecular weight is those of 300-2400.
Illustrate in greater detail the present invention according to synthesis example and example application again below the present invention and contain the polymerisable functional high-polymer bonding agent of the ethene unsaturated group with structure i and ii, more its technical scheme of sets forth in detail.But these do not limit protection scope of the present invention.
Synthesis example 1
In the 250ml there-necked flask that has stirrer, recirculatory pipe, tap funnel, add 20g MEK, 0.18g azo-bis-isobutyl cyanide.Utilize hot bath to be heated to 80 ℃ on one side, on one side logical nitrogen protection.The mixed solution that dropping is made up of 20g MEK, 3.5gN-(4-hydroxy benzenes) Methacrylamide, 4.5gN-(4-sulfoamido benzene) maleimide, 4.5g styrene, 3.0 gram methacrylic acids dropwised in 2 hours.Constant temperature reacted 10 hours down.Reaction finishes the back and adds 40g methyl alcohol, and cooling joins in the 2L water under stirring, and stirs filtration drying after 1 hour, obtains the 12.98g white solid.Utilizing the silica gel permeation chromatography to measure the weight average molecular weight of this high molecular polymer (polystyrene standard) is 45000.
The above-mentioned gained superpolymer of 10 grams is dissolved in the only methyl ether acetate of 100 gram propylene glycol, adds 0.05 gram p-dihydroxy-benzene while stirring, 0.2 gram chromium acetylacetonate is warming up to 90 ℃ under the nitrogen protection, drip 2 milliliters of bromopropenes, isothermal reaction 3 hours.Be distributed to after the cooling and get 9.8 gram white solids in the 2L water.Standby behind the filtration drying.Acid number is 66mg KOH/g.
Synthesis example 2:
In the 500ml four-hole bottle that has stirrer, recirculatory pipe, tap funnel, add 20gN, dinethylformamide, 1.8g azo-bis-isobutyl cyanide.Utilize hot bath to be heated to 80 ℃ on one side, on one side logical nitrogen protection.Dropping is by 130g N, the mixed solution that dinethylformamide, 1g N-(4-hydroxy benzenes) Methacrylamide, 8g N-(4-sulfoamido benzene) maleimide, 25g N-(4-acetyl oxygen phenyl) maleimide, 48g methyl methacrylate, 18 gram methacrylic acids are formed dropwised in 2 hours.Constant temperature reacted 10 hours down.Reaction finishes the back and adds 200g methyl alcohol, and cooling joins in the 2L water under stirring, and stirs filtration drying after 1 hour, obtains the 90.98g white solid.Utilizing the silica gel permeation chromatography to measure the weight average molecular weight of this high molecular polymer (polystyrene standard) is 54000.
The above-mentioned gained superpolymer of 50 grams is dissolved in the only methyl ether acetate of 500 gram propylene glycol; add 0.25 gram p methoxy phenol while stirring, 2 gram chromium acetylacetonates are warming up to 90 ℃ under the nitrogen protection; drip 20 milliliters of glyceral methacrylate, isothermal reaction 3 hours.Be distributed to after the cooling and get 53 gram white solids in the 20L water.Standby behind the filtration drying.Acid number is 56mg KOH/g.
Synthesis example 3:
In the 500ml four-hole bottle that has stirrer, recirculatory pipe, tap funnel, add the positive butanone of 20g, 1.8g benzoyl peroxide.Utilize hot bath to be heated to 75 ℃ on one side, on one side logical nitrogen protection.Dropping is by 130g N, the mixed solution that dinethylformamide, 30g N-(4-hydroxy benzenes) Methacrylamide, 10g N-(4-sulfoamido benzene) maleimide, 1g N-(4-acetyl oxygen phenyl) maleimide, 35g methyl methacrylate are formed, the 15g methacrylic acid dropwised in 2 hours.Constant temperature reacted 10 hours down.Reaction finishes the back and adds 200g methyl alcohol, and cooling joins in the 2L water under stirring, and stirs filtration drying after 1 hour, obtains the 90.00g white solid.Utilizing the silica gel permeation chromatography to measure the weight average molecular weight of this high molecular polymer (polystyrene standard) is 64000.
The above-mentioned gained superpolymer of 50 grams is dissolved in the only methyl ether acetate of 500 gram propylene glycol; add 0.23 gram p methoxy phenol while stirring, 1.8 gram chromium acetylacetonates are warming up to 90 ℃ under the nitrogen protection; drip 13 milliliters of glyceral methacrylate, isothermal reaction 3 hours.Be distributed to after the cooling and get 53 gram white solids in the 20L water.Standby behind the filtration drying.Acid number is 60mg KOH/g.
Synthesis example 4:
In the 500ml four-hole bottle that has stirrer, recirculatory pipe, tap funnel, add 20gN, dinethylformamide, 1.8g benzoyl peroxide.Utilize hot bath to be heated to 75 ℃ on one side, on one side logical nitrogen protection.Dropping is by 130g N, dinethylformamide, 20g N-(4-sulfoamido benzene)) mixed solution that Methacrylamide, 25g N-(4-hydroxy benzenes) maleimide, 40 gram styrene, 15 gram methacrylic acids are formed, dropwised in 2 hours.Constant temperature reacted 10 hours down.Reaction finishes the back and adds 200g methyl alcohol, and cooling joins in the 2L water under stirring, and stirs filtration drying after 1 hour, obtains the 92.98g white solid.Utilizing the silica gel permeation chromatography to measure the weight average molecular weight of this high molecular polymer (polystyrene standard) is 50000.
The above-mentioned gained superpolymer of 50 grams is dissolved in the only methyl ether acetate of 500 gram propylene glycol; add 0.25 gram p methoxy phenol while stirring, 2 gram chromium acetylacetonates are warming up to 90 ℃ under the nitrogen protection; drip 20 milliliters of glyceral methacrylate, isothermal reaction 3 hours.Be distributed to after the cooling and get 53 gram white solids in the 20L water.Standby behind the filtration drying.Acid number is 53mg KOH/g.
Synthesis example 5:
In the 500ml four-hole bottle that has stirrer, recirculatory pipe, tap funnel, add 20gN, dinethylformamide, 1.8g benzoyl peroxide.Utilize hot bath to be heated to 75 ℃ on one side, on one side logical nitrogen protection.Dropping is by 130g N, dinethylformamide, 30g N-(4-sulfoamido benzene)) mixed solution that Methacrylamide, 35g styrene, 15 gram methacrylic acids, 20g N-(4-acetyl oxygen phenyl) maleimide are formed, dropwised in 2 hours.Constant temperature reacted 10 hours down.Reaction finishes the back and adds 200g methyl alcohol, and cooling joins in the 2L water under stirring, and stirs filtration drying after 1 hour, obtains the 89.25g white solid.Utilizing the silica gel permeation chromatography to measure the weight average molecular weight of this high molecular polymer (polystyrene standard) is 58000.
The above-mentioned gained superpolymer of 50 grams is dissolved in the only methyl ether acetate of 500 gram propylene glycol, adds 0.25 gram p-dihydroxy-benzene while stirring, 1.2 gram chromium acetylacetonates are warming up to 90 ℃ under the nitrogen protection, drip 10 milliliters of bromopropenes, isothermal reaction 3 hours.Be distributed to after the cooling and get 9.8 gram white solids in the 2L water.Standby behind the filtration drying.Acid number is 62mg KOH/g.
With reference to synthesis example 1-5, synthesize the polymerisable functional high-polymer bonding agent of following table 1-4 ethene unsaturated group.(seeing Table one)
The polymerisable functional high-polymer adhesive application of ethene unsaturated group of the present invention in the thermal polymerization lithographic plate, can be produced the photosensitive lithographic plate that contains this polyvinyl in the heat-sensitive layer.
With embodiment the present invention is carried out specific description more below, but the present invention is not limited to this.The version base is handled
Using No. 8 nylon brusses and 800 purpose float stone aqueous suspensions, is that water cleaned fully after the surface of aluminum plate of 0.3mm was carried out graining to thickness.In 10% NaOH, after 70 ℃ dipping carried out etching in 60 seconds down, clean, use 20%HNO afterwards with flowing water
3Washing, washing neutralize.At V
AUse under the condition of=12.7V sinusoidal wave alternately waveform electric current in 1% aqueous solution of nitric acid with 300 coulombs/dm
2Anode the time electric weight it is carried out the processing of electrolysis asperities.Measure its surperficial Grains situation, the result is 0.45um (representing with Ra).Then be immersed in 30% H
2SO
4In the aqueous solution, 55 ℃ of following decontaminations after 2 minutes, at 33 ℃, 20%H
2SO
4In the aqueous solution, disposing negative electrode on the face that has carried out graining, is 5A/dm in current density
2Condition under carry out 50 seconds of anodizing, thickness is 3.0g/m as a result
2
The formation in middle layer
Through on the aluminium sheet of above-mentioned processing, apply the polyvinyl phosphonic acids.The thickness in this middle layer is 3mg/m
2
Then, apply following sensitization liquid with getting rid of an edition method on this base version, 110 ℃ were descended dry 1 minute, and obtained sensible heat type flat stamping version.Dried coating weight is about 2.0g/m2.
Sensitization liquid
Sartomer 399 (polyfunctional group acrylic monomers; Startomer Co., Inc.)
1.5 gram
Synthetic resin 2.0 grams
2-(4-methoxyphenyl)-4, two (trichloromethyl)-s-triazine 0.3 grams of 6-
2-[2-[2-thiophenyl-3-[2-(1,3-dihydro-1,3,3-trimethyl one 2H-indoline-2-subunit)-ethylidene]-1 one cyclohexene-1-yl]-vinyl]-1,3,3-trimethyl-3H-indoles chloride 0.04 gram
2,2/-di-2-ethylhexylphosphine oxide (4-methyl-6-tert butyl phenol) 0.01 gram
Alkaline bright blue 0.03 gram
Fluorochemical surfactant 0.02 gram
MEK 20 grams
Cyclohexanone 13 grams
1-methoxyl-2-propyl alcohol 27 grams
Adopt the Wound-rotor type scraper, make the above-mentioned solution of coating on surperficial roughening and the anodized aluminium with electrochemical method, obtain the dry coating weight of 2g/m2.In the baking oven of tape drum wind, in about 94 ℃ of down dry about 120 seconds residence time of this forme.Prepare external coating solution by 5.26 parts of Japanese Kuraray PVA203,0.93 part of polyvinyl imidazol, 3.94 parts of isopropyl alcohols and 89.87 parts of water.With after applying external coating with the similar mode of undercoat, in the baking oven of tape drum wind, in about 94 ℃ of down dry about 150 seconds residence time of this forme.The dry coating weight of external coating is similarly 2g/m2.Expose on the direct platemaking machine of the LOTEM400 of Creo company temperature-sensitive, laser intensity is to make these forme imagings under 180 milliwatts.This serial plate sensitivity is 100mJ/cm2.After becoming image ground exposure printing plate precursor, it not necessarily can be heated to about 80 ℃-Yue 130 ℃ temperature in the short time period, so that carry out the full solidification of exposure region.This time that need spend was depended on the temperature that is applied, about only 20 seconds-Yue 100 seconds.Then, by method known to those skilled in the art,, forme is developed as at described in the United States Patent (USP) NO.5035982 those.Afterwards, available everybody known pipe protection glue is handled the forme that has developed.
The lithographic printing plate-use UV ink printing that use obtains, the seal journey can reach more than 100,000 impressions.
Application result by table 2 shows, in sensible heat flat stamping version of the present invention, contain have above-mentioned (a) and (b), the multipolymer of (c) expression structural unit, make that thus flat stamping version of the present invention has strong adhesion, coating is tough and tensile; The superpolymer dissolubility is good, so the coating in when coating is good on support.Flat stamping version of the present invention has that good printing-force-resistence, development tolerance are big, alkali resistant membrane left rate height, solvent resistance are strong.Can get the printed matter of image fineness when using the UV ink printing.
Table one
| The flat stamping version | Use superpolymer | Anti-isopropyl alcohol (%) | Plate sensitivity (mJ/cm2) | Pressrun (UV ink printing) | Comprehensive evaluation |
| Flat stamping version 1 | 1 | 92 | 102 | 120000 | Excellent |
| Flat stamping version 2 | 2 | 90 | 99 | 105000 | Excellent |
| Flat stamping version 3 (comparative example) | 3 | 80 | 105 | 36000 | Very |
| Flat stamping version (comparative example) | 4 | 70 | 96 | 32000 | Very |
Table two
Claims (9)
1, a kind of thermosensitive polymerized lithographic printing plate is characterized in that: it comprises support and thermal polymerization layer, and wherein the thermal polymerization layer includes the polymerisable functional high-polymer bonding agent of the ethene unsaturated group with structure i and ii (A); Functional high-polymer adhesive construction with structure i and ii is as follows:
I has following two kinds of structures (a), and (b) unit is one of any:
(a) has alkali-soluble structural unit
In the formula X1 represent-O-or-NR3-, R1 represents-H or-CH3, what R2 represented singly-bound or divalent has a switch base, Y1 represents arylene, n represents 0 or 1, R3 represents to have alkyl, naphthenic base, the aryl or aralkyl of a hydrogen atom or a substituent 1-12 carbon atom; Z1 represents to have the group of acid hydrogen atom, and m represents the integer more than 1;
(b) has the structural unit of alkali-soluble maleimide
Z represents to have the group of acid hydrogen atom, can be-COOH ,-OH or-SO2NH2;
Ii has the carboxylic acid esters structure that acid causes phase transition property:
R represents alkyl, naphthenic base, aralkyl.
2, thermosensitive polymerized lithographic printing plate according to claim 1, it is characterized in that: described wherein thermal polymerization layer contains the polymerisable functional high-polymer bonding agent of the ethene unsaturated group with structure i and ii (A), also contain: unsaturated free radical polymerization monomer and oligomer (B), can absorbing IR the infrared absorbent (C) of ray, can produce at least a thermal polymerization (D) of free radical.
3, thermosensitive polymerized lithographic printing plate according to claim 1 and 2, it is characterized in that: the quality of compound unit in high molecular polymer that has the alkali solubility group shown in described containing (a) is 0-60% than content, be preferably 10-30%, containing the quality of compound unit in high molecular polymer that has the alkali solubility group shown in (b) is 0-60% than content, be preferably 10-30%, containing the quality of the compound unit shown in (c) in high molecular polymer is 1-50% than content, is preferably 10-25%.
4, thermosensitive polymerized lithographic printing plate according to claim 1 and 2, it is characterized in that: the weight average molecular weight of described polyvinyl is more than 3000, be preferably 5000-20 ten thousand, number-average molecular weight is at 1500 above high molecular polymers, be preferably 3000-20 ten thousand, dispersion degree is greater than 1.4.
5, thermosensitive polymerized lithographic printing plate according to claim 1 and 2 is characterized in that: described polyvinyl total acid number is 70mg KOH/g or lower.
6, thermosensitive polymerized lithographic printing plate according to claim 1 and 2, it is characterized in that: described can absorbing IR the infrared absorbent (C) of ray, the infrared absorbent of this IR ray contains a kind of of dyestuff that the absorption maximum scope is 760-1200nm and pigment.
7, thermosensitive polymerized lithographic printing plate according to claim 1 and 2 is characterized in that: the infrared absorbent (C) of described energy absorbing IR ray is
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, SO
2R, OR or NR
2
Each R
3Can be hydrogen, alkyl, COOR, OR, SR, SO independently
3 -, NR
2, halogen and the fused benzo ring that not necessarily replaces;
A
-The expression negative ion;
---expression nonessential five yuan or six-membered carbon ring;
Wherein each R can be hydrogen, alkyl and aryl independently; With
Wherein each n can be 0,1,2 or 3 independently.
8, thermosensitive polymerized lithographic printing plate according to claim 1 and 2 is characterized in that: described thermal polymerization (D) preferably comprises compound in triazine class.
9, thermosensitive polymerized lithographic printing plate according to claim 1 and 2 is characterized in that: described thermosensitive polymerized lithographic printing plate can also comprise and is selected from salt compounded of iodine, diazo salt and sulfosalt as thermal polymerization (D).
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103370198A (en) * | 2011-02-18 | 2013-10-23 | 爱克发印艺公司 | A lithographic printing plate precursor |
| CN106519116A (en) * | 2016-11-05 | 2017-03-22 | 中国乐凯集团有限公司 | Resin for positive-acting thermosensitive CTP plate coating layer |
| CN107778911A (en) * | 2017-08-29 | 2018-03-09 | 中国乐凯集团有限公司 | A kind of IR absorbing dye and its application |
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| US5262500A (en) * | 1991-10-23 | 1993-11-16 | Tatung Co. | Preparation of novel silicon-containing photoresists for use in IC microlithography |
| JP4248137B2 (en) * | 2000-11-22 | 2009-04-02 | 富士フイルム株式会社 | Negative photosensitive lithographic printing plate |
| CN1301276C (en) * | 2001-09-25 | 2007-02-21 | 大日本印刷株式会社 | Alkali-soluble maleimide copolymer and liquid crystal display comprising the same |
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2005
- 2005-12-23 CN CNB2005101073072A patent/CN100570481C/en active Active
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103370198A (en) * | 2011-02-18 | 2013-10-23 | 爱克发印艺公司 | A lithographic printing plate precursor |
| CN106519116A (en) * | 2016-11-05 | 2017-03-22 | 中国乐凯集团有限公司 | Resin for positive-acting thermosensitive CTP plate coating layer |
| CN107778911A (en) * | 2017-08-29 | 2018-03-09 | 中国乐凯集团有限公司 | A kind of IR absorbing dye and its application |
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