CN1946753A - Positive-working, thermally sensitive imageable element - Google Patents
Positive-working, thermally sensitive imageable element Download PDFInfo
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- CN1946753A CN1946753A CN 200580012150 CN200580012150A CN1946753A CN 1946753 A CN1946753 A CN 1946753A CN 200580012150 CN200580012150 CN 200580012150 CN 200580012150 A CN200580012150 A CN 200580012150A CN 1946753 A CN1946753 A CN 1946753A
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Abstract
Alkali solute copolymers, imageable elements useful as lithographic printing plate precursors that contain the alkali solute copolymers, and methods for forming images using the imageable elements are disclosed. The alkali soluble copolymers comprise, in polymerized form: (a) N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, or a mixture thereof; (b) acrylamide, methacrylamide, or a mixture thereof; (c) acrylonitrile, methacrylonitrile, or a mixture thereof; and (d) one or more monomers selected from the group consisting of monomers of the structure: CH2=C(R)-Z-X-NHC(O)NH-Y-R', in which: X is -[C (CH3)2]- or -[(CH2)n]-, in which n is 0 to 12; Y is o-, m-, or p- -[C6H4]-; Z is -[C(O)O]-, -[C(O)NH]-, or o-, m-, or p-[-C6H4]-; R is hydrogen or C1 to C4 alkyl; R' is -OC(O)-OR'', -OC(O)-Ar, or -OSO2-Ar; R'' is C1 to C12 alkyl, C1 to C12 arylalkyl, C1 to C12 aryl, C1 to C12 alkenyl, or trimethylsilyl; Ar is C6H5-n'Tn', in which Ar has a total of six to ten carbon atoms, each T is independently selected from the group consisting of C1 to C4 alkyl, fluoro, chloro, bromo, iodo, trifluoromethyl, methoxy, and cyano; and n' is an integer from 0 to 5; and in which the copolymer is soluble in alkaline solutions having a pH greater than at least about 11.
Description
Invention field
The present invention relates to lithography.More particularly, the present invention relates to the imageable element that contains the alkali soluble multipolymer, can be used as lithographic printing plate precursor.
Background of invention
Routine or " wet method " lithography in, the printing ink region of acceptance that is known as image area is formed on the water-wetted surface.When this surface by water-wet and when being subjected to printing ink, hydrophilic region keeps water and repels printing ink, and printing ink region of acceptance picks up ink and repel water.With ink transfer will duplicating image on it a material surface.Usually, printing ink at first is transferred to bed course in the middle of, its in turn with ink transfer will duplicating image on it described material surface.
The imageable element that can be used as lithographic printing plate precursor generally includes the imageable layer that is applied to the base material water-wetted surface.This imageable layer comprises that one or more can be scattered in the radiation sensitive component in the suitable tackiness agent.Selectively, this radiation sensitive component also can be an adhesive material.After the imaging, remove the imaging region of imageable layer or imaging region not, expose the bottom water-wetted surface of base material by suitable photographic developer.If what remove is imaging region, then this precursor is an eurymeric.Otherwise if what remove is imaging region not, then this precursor is a minus.In all cases, remaining imageable layer zone (being image area) but picks up ink, and the water-wetted surface that exposes by developing process zone absorbs the water and the aqueous solution, is generally wetting liquid (fountainsolution), and repels printing ink.
Exempted and to have come the Direct Digital of imaging to be imaged on to become in the Printing industry to become more and more important by mask.Now but the eurymeric thermal imaging element that needs should develop under conventional high pH developer and can toast and tolerate the printing chemical reagent, for example printing ink, wetting liquid and be used to clean solvent as the UV cleaning.Expect that very it has the property of baking, because bake process has improved print stroke.Therefore, but need in high pH developer, to develop, can tolerate the chemical reagent that in the printing office environment, can run into usually, and can toast thermal imaging element with the raising stroke.
The invention summary
On the one hand, the present invention is a kind of alkali soluble multipolymer.This multipolymer comprises the following material of polymerized form:
(a) 1wt% is to the N-phenylmaleimide of 30wt%, N-cyclohexyl maleimide, N-benzyl maleimide or its mixture;
(b) about 1wt% is to acrylamide, Methacrylamide or its mixture of about 30wt%;
(c) about 20% to about 75% vinyl cyanide, methacrylonitrile or its mixture; And
(d) the about 20wt% of total amount is selected from the monomeric monomer of following structure to one or more of about 75wt%:
CH
2＝C(R)-Z-X-NHC(O)NH-Y-R’
Wherein:
X is-[C (CH
3)
2]-or-[(CH
2)
n]-, wherein n is 0 to 12;
Y be adjacent-,-or right-[C
6H
4]-;
Z is-[C (O) O]-,-[C (O) NH]-or adjacent-,-or right-[C
6H
4]-;
R is hydrogen or C
1To C
4Alkyl;
R ' is-OC (O)-OR " ,-OC (O)-Ar or-OSO
2-Ar;
R " be C
1To C
12Alkyl, C
1To C
12Aralkyl, C
1To C
12Aryl, C
1To C
12Thiazolinyl or trimethyl silyl;
Ar is C
6H
5-n 'T
N ', wherein the total number of carbon atoms of Ar is six to ten;
Each T is independently selected from C
1To C
4Alkyl, fluoro, chloro, bromo, iodo, trifluoromethyl, methoxyl group and cyano group; And
N ' is 0 to 5 integer; And
Wherein this multipolymer dissolves in the pH value greater than about at least 11 basic solution.
On the other hand, the present invention is a kind of imageable element that comprises this alkali soluble multipolymer.This imageable element that can be used as lithographic printing plate precursor can be the imageable element or the multiwalled imageable element of individual layer.Also have on the one hand, the present invention is a kind of by making described imageable element imaging and development form the method for image.
Detailed Description Of The Invention
Unless point out in addition in the literary composition, in specification sheets and claim, term first tackiness agent, second tackiness agent, resol, tensio-active agent, novolac resin, optical-thermal conversion material, dissolution inhibitor, alkali soluble multipolymer, coating solvent and similar term also comprise these mixtures of material.Unless otherwise indicated, all per-cents are weight percentage.Thermal imaging refers to utilize hot body such as thermal head or utilizes the ir radiation imaging process.
Although defined multipolymer according to the conceptive monomer that can be used to form multipolymer, this does not make multipolymer be limited to the multipolymer that those form by said monomer polymerization.Multipolymer can form by other method.The for example modification by precursor polymer.For example, multipolymer can be by adding various side-chain structures unit in precursor polymer, as carbonic ether (OC (O)-OR ") group, ester (OC (O)-Ar) group and/or sulphonate (O
3SAr) group.The alkali soluble multipolymer dissolves in the pH value greater than in about at least 11 the basic solution, typically dissolves in the pH value greater than in about at least 12 the basic solution, more typically dissolve in the pH value about 12 in about 14 basic solution.
The alkali soluble multipolymer comprises polymerized form, and approximately 1wt% is to about 30wt%, and preferably approximately 3wt% is to the N-phenylmaleimide of about 20wt%, N-cyclohexyl maleimide, N-benzyl maleimide or its mixture.Preferred N-phenylmaleimide.
The alkali soluble multipolymer comprises polymerized form, and approximately 1wt% is to about 30wt%, and preferably approximately 5wt% is to acrylamide, Methacrylamide or its mixture of about 20wt%.The preferable methyl acrylamide.
The alkali soluble multipolymer comprises polymerized form, and approximately 20wt% is to about 75wt%, and preferably approximately 35wt% is to vinyl cyanide, methacrylonitrile or its mixture of about 60wt%.Preferred vinyl cyanide.
The alkali soluble multipolymer comprise polymerized form, to about 75wt%, preferably approximately 30wt% is selected from the monomer of following structure to one or more of about 60wt% to total amount at about 20wt%:
CH
2＝C(R)-Z-X-NHC(O)NH-Y-R’
X is-[C (CH
3)
2]-or-[(CH
2)
n]-, wherein n is 0 to 12.When X is-[(CH
2)
n]-and n be 0 o'clock, the direct key of Z group is ined succession-NHC (O) NH-Y-R ' group.The preferred group of X comprises-[C (CH
3)
2]-or-[(CH
2)
2]-.
Y is phenylene-[C
6H
4]-.Described phenylene can adjacent, or contraposition be substituted.The preferred group of Y comprises the phenylene (p-[C of para-orientation
6H
4]-).
Z is-[C (O) O]-,-[C (O) NH]-or phenylene ([C
6H
4]-), its can adjacent, or contraposition be substituted.The preferred group of Z comprises-[C (O) O]-and the phenylene (m-[C that replaces of a position
6H
4]-).
R is hydrogen or C
1To C
4Alkyl.Typical C
1To C
4Alkyl is methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl and the tertiary butyl for example.The preferred group of R comprises hydrogen and methyl.Methyl is more preferred.
R ' is-OC (O)-OR " ,-OC (O)-Ar or-OSO
2-Ar.
R " be C
1To C
12Alkyl, C
1To C
12Aryl or substituted aryl, C
1To C
12Aralkyl, C
1To C
12Aryl, C
1To C
12Thiazolinyl or trimethyl silyl.Typical C
1To C
12Alkyl comprises, methyl for example, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, isopentyl, sec.-amyl sec-pentyl secondary amyl, 1,1-dimethyl propyl, 2, the 2-dimethyl propyl, n-hexyl, 1,1-dimethylbutyl, n-heptyl, 1,1-dimethyl amyl group, 2-ethyl pentyl group, 5-methyl hexyl, n-octyl, 1,1-dimethyl hexyl, 2,2,4-tri-methyl-amyl, 1,1,3,3-tetramethyl butyl, 2-ethylhexyl, n-nonyl, 1,1-dimethyl heptyl, positive decyl, 1,1-dimethyl octyl group, n-undecane base, 1,1-dimethyl nonyl, dodecyl, and 1, the 1-dimethyl decyl.Typical C
1To C
12Aryl and substituted aryl comprise, phenyl, 1-naphthyl, 2-naphthyl, p-methylphenyl, a tolyl, o-tolyl, p-methoxyphenyl, m-methoxyphenyl, guaiacyl, to phenelyl, to the ethylbenzene base, to cumyl, to trimethylphenylmethane base, rubigan, to bromophenyl, to cyano-phenyl, a cyano-phenyl, to fluorophenyl, pentafluorophenyl group, five chlorophenyl, p-trifluoromethyl phenyl, 3,5-dichlorophenyl, 3,5-xylyl, 3,5-diethyl phenyl and 2,4, the 6-trimethylphenyl.Typical C
1To C
12Aralkyl for example comprises, phenmethyl, 1-styroyl, the 2-styroyl, 2-hydrocinnamyl, 1-phenyl-1-methylethyl, 1-phenyl-1-methylethyl, 3-hydrocinnamyl, 4-phenyl butyl, 2-phenyl-1, the 1-dimethyl ethyl, 1-phenyl-1-methyl-propyl, 6-phenyl hexyl, and 4-phenyl-1, the 1-dimethylbutyl.Typical C
1To C
12Thiazolinyl for example comprises, allyl group (2-propenyl) (CH
2=CH-CH
2-), 1-methacrylic (CH
2=CH-C (CH
3) H-), 1,1-dimethyl-allyl (CH
2=CH-C (CH
3)
2-), 1-methyl-3-butenyl (CH
2=CH-CH
2-C (CH
3) H-), 1-methyl-2-butene base (CH
3CH=CH-C (CH
3) H-), 1,1-dimethyl-3-butenyl (CH
2=CH-CH
2-C (CH
3)
2-), and 1,1-dimethyl-9-decene base (CH
2=CH-(CH
2)
7-C (CH
3)
2-).R " preferred group comprises the tertiary butyl, phenyl, 1-phenylethyl (CH
3-CH (C
6H
5)-), phenmethyl, 1-methacrylic and trimethyl silyl.More preferred carbonate group is tertiary butyl carbonic ether (t-BOC) group, wherein R " be the tertiary butyl.
Ar is C
6H
5-n 'T
N ', wherein the total number of carbon atoms of Ar is six to ten.Six to ten carbon atoms of sum had both comprised the carbon atom in the hexa-atomic aromatic hydrocarbons system, also comprised the carbon atom that may be present in the substituted radical in the aromatic hydrocarbons system, for example the carbon atom in methyl, ethyl, propyl group, butyl, trifluoromethyl, cyano group and the methoxyl group.For example 4-tolyl (p-methylphenyl or tosyl group) group has seven carbon atoms.Each T is independently selected from following group: C
1To C
4Alkyl, fluoro, chloro, bromo, iodo, trifluoromethyl, methoxyl group and cyano group.C
1To C
4Alkyl for example comprises, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl and the tertiary butyl.N ' is 0 to 5 integer.For example, when n ' was 0, Ar was a phenyl.When n ' is 1 and T when being methyl, Ar is p-methylphenyl (tosyl group), a phenmethyl or adjacent phenmethyl.When n ' is 5 and each T when being fluoro, Ar is a pentafluorophenyl group.Typical A r base for example comprises phenyl, p-methylphenyl (tosyl group), a tolyl, o-tolyl, p-methoxyphenyl, m-methoxyphenyl, guaiacyl, to phenelyl, to ethylbenzene base, p-isopropyl phenyl, to tert-butyl-phenyl, rubigan, to bromophenyl (p-bromobenzenesulfonyl), to cyano-phenyl, a cyano-phenyl, to fluorophenyl, five chlorophenyl, p-trifluoromethyl phenyl, 3; 5-dichlorophenyl, 3; 5-xylyl, 3; 5-diethyl phenyl, 3; 5-two (trifluoromethyl) phenyl and 2; 4, the 6-trimethylphenyl.Because each T is independent the selection, so can there be the substituting group of more than one types in the aromatic hydrocarbons system.For example, Ar can be 4-fluoro-2,6-dichlorophenyl, 4-methyl-3,5-dichlorophenyl, 4-bromo-2,6-3,5-dimethylphenyl or 4-methyl-3-cyano-phenyl.The preferred group of Ar is phenyl and 4-tolyl (tosyl group).
The alkali soluble multipolymer can comprise one or more other monomers of polymerized form.The monomer that contains ionogen can be used for improving or controls the solubility feature of multipolymer in aqueous alkali.For example, multipolymer can comprise 5wt% polymerized form, about to about 30wt%, and preferably approximately 10wt% is to vinylformic acid, methacrylic acid or its mixture of about 30wt%.Other monomer in addition for example comprises, the acrylamide of benzaminic acid or Methacrylamide are as the acrylamide or the Methacrylamide (CH of para-amino benzoic acid
2=C (R)-CONH-p-C
6H
4-CO
2H), and by cyclic acid anhydride, as the acrylate or the methacrylic ester of succinyl oxide or Tetra hydro Phthalic anhydride and hydroxyl, for example 2-hydroxyethyl meth acrylate or 2-hydroxy ethyl methacrylate (CH
2=C (R)-CO
2-CH
2CH
2-O
2C-W-CO
2The half ester that the H reaction forms, wherein W is-[(CH
2)
2)
2]-or-[o-C
6H
4]-).
The alkali soluble multipolymer can pass through prepared in various methods.Below list some and can prepare their mode.Obviously also has alternate manner to those skilled in the art.
For example, can prepare multipolymer by Raolical polymerizable.Raolical polymerizable is known to those skilled in the art, for example exists
Macromolecules, second edition the 2nd volume, H.G.Elias, Plenum, New York describes in 1984 the 20th and 21 chapters to some extent.The radical initiator that is suitable for has superoxide such as benzoyl peroxide, and hydroperoxide such as peroxide hydrogenation isopropyl benzene and azo-compound are as 2, and 2 '-azo two (isopropyl cyanide) (AIBN).Chain transfer agents can be used for controlling the molecular weight of multipolymer as dodecyl mercaptans.The suitable solvent that is contained in radical polymerization process comprises reactant is inertia and can not cause the liquid of disadvantageous effect conversely to reaction, for example ester such as ethyl acetate and butylacetate; Ketone is methylethylketone for example, methyl iso-butyl ketone (MIBK), methyl propyl ketone and acetone; Alcohol is methyl alcohol, ethanol, Virahol and butanols for example; Ether is two alkane and tetrahydrofuran (THF)s for example, with and composition thereof.
Monomer can carry out polymerization to produce the alkali soluble multipolymer of expection with predetermined amount.
For example, contain monomeric isocyanic ester, for example isocyanic acid alkyl acrylate or its methacrylic ester, for example isocyanic acid ethyl-methyl acrylate, perhaps contain the cinnamic isocyanic ester that alkyl replaces, for example 1-(1-isocyanic acid-1-methyl)-ethyl 3-(1-methyl)-vinyl benzene (CH
2=C (CH
3)-m-C
6H
4-C (CH
3)
2-NCO), can form urea with suitable aromatic amine reaction.Before urea forms or carbonate group can be added amine afterwards.The formation and the conversion of these monomers to the polymkeric substance that contains carbonate group of the carbonic ether that contains free radical polymerizable monomer are disclosed in the U.S. Patent No. 4491628 of for example Ito.
Perhaps, the alkali soluble multipolymer can form by the modification of precursor polymer.For example, contain monomeric isocyanic ester, for example top listed, can carry out the copolymerization reaction and produce the precursor polymer that contains the isocyanate functional group.At U.S. Patent No. 4565759 the 8th hurdle the 61st of for example Dueber row the polymerization that contains monomeric isocyanic ester is disclosed and in order to functional group is introduced the isocyanato reaction in the resulting polymers in the 10th hurdle the 52nd row.Precursor polymer can generate the polymkeric substance of expection with the suitable carbonic ether that contains aromatic amine or amine, ester and/or sulphonate reaction then.Perhaps, urea functional group and carbonic ether, ester or sulfonate functionality can be introduced in dividing other step.For example, the isocyanic ester that contains precursor polymer can generate second precursor polymer with aromatic amine such as p-aminophenol reaction, and it contains the phenolic hydroxyl group group.The phenolic hydroxyl group group can be converted into carbonic ether, ester and/or sulfonate ester group.
Perhaps, precursor polymer can be by containing monomeric phenolic hydroxyl group preparation.The monomeric phenolic hydroxyl group that contains that is suitable for for example comprises:
The monomer that contains one or more monomeric phenolic hydroxyl groups and other expection carries out copolyreaction and generates the precursor polymer that contains phenolic hydroxyl group.This order is listed in the synthetic embodiment 2,4 and 5 of for example U.S. Patent No. 6352811.Then phenolic hydroxyl group is converted to carbonate group, ester class group and/or sulfonate ester group.The phenolic hydroxyl group utilization can be well known to a person skilled in the art method converts carbonate group to.For example, can introduce tertiary butyl carbonic ether (t-BOC) group by the multipolymer and the di-tert-butyl dicarbonic acid ester reaction under the situation of salt of wormwood and 18-crown-6 existence that contain phenolic hydroxyl group.By for example with carboxylic acid halides, mixture reaction as acyl chlorides or acyl chlorides forms ester group or ester group mixture, and/or and sulfonic acid halide, form sulfonate ester group or sulfonate ester group mixture as SULPHURYL CHLORIDE or SULPHURYL CHLORIDE mixture reaction, phenolic hydroxyl group can be converted to ester (OC (O)-Ar) group and/or sulphonate (O
3SAr) group.Typical carboxylic acid halides for example, Benzoyl chloride, adjacent anisyl chloride, between anisyl chloride, p-anisoyl chloride, toluoyl chlorine, toluoyl chlorine, P-Toluoyl chloride, 2-bromo-benzoyl chloride, the 3-bromo-benzoyl chloride, 4-bromo-benzoyl chloride, 2-chloro-benzoyl chloride, the 3-chloro-benzoyl chloride, 4-chloro-benzoyl chloride, p-isopropylbenzoyl chlorine, 3, two (trifluoromethyl) Benzoyl chlorides of 5-and right-(trifluoromethyl) Benzoyl chloride.Preferred acyl chlorides has Benzoyl chloride and Butyltriphenylphosphonium chloride.Typical sulfonic acid halide for example has benzene sulfonyl chloride, Tosyl chloride, 4-chlorobenzene sulfonyl chloride, 4-bromobenzene sulfonyl chloride, 4-fluorobenzene SULPHURYL CHLORIDE and 4-anisole SULPHURYL CHLORIDE.Preferred SULPHURYL CHLORIDE is benzene sulfonyl chloride and Tosyl chloride.
The alkali soluble multipolymer can be used in the eurymeric imageable element.Imageable element comprises imageable layer or the top layer that is positioned on the substrate surface, but it comprises image forming composition.Can also there be other layer as conventional each component of imageable element.For example, imageable layer can be on base material, and perhaps other layer may reside between imageable layer and the base material as bottom.Imageable element can also comprise optical-thermal conversion material, it can be present in imageable layer, bottom or the independent absorber layer, if bottom exists this independent absorber layer between imageable layer and bottom, if do not have bottom its between imageable layer and base material.Yet imageable element does not comprise the acidogenic agent of thermal activation usually.
Base material comprises carrier, and it can be any material that is generally used for preparing as the imageable element of planographic printing plate.Carrier preferably has stability, stability and snappiness.Its size that should bear under working conditions changes, and makes that color record will be with the mode alignment of full-color image.Typically, it can be any self-bearing type (self-supporting) material, for example comprises the laminate of polymeric film such as polyethylene terephthalate film, pottery, metal or carton paper (stiffpaper) or any of these material.Metallic carrier comprises aluminium, zinc, titanium and alloy thereof.
Typically, polymeric film contains down coating with modified surface character on one or both sides, thus strengthen this surperficial wetting ability, raising and follow-up each layer tackiness, improve planeness of paper base material or the like.The character of this layer or these layers depends on the composition of base material and follow-up each layer.The example of glue-line material has the material of tackifying, and as organoalkoxysilane, aminopropyl triethoxysilane, glycidyl ether oxygen base propyl-triethoxysilicane and epoxide function fluidized polymer, and is used for conventional glue-line material on the polyester based in the photo film.
The surface of alumina supporter can be handled by technology known in the art, comprises physics granulation, electrochemistry granulation, chemical granulation and anodizing.Base material should have enough thickness bearing the wearing and tearing in the printing process, and should enough approach with around the cylinder of living in the printing press, it typically is about 100 μ m to about 600 μ m.Typically, base material is included in the middle layer between alumina supporter and one or more layers lamination.Can make the middle layer by handling alumina supporter with for example silicate, dextrin, hexafluorosilicic acid, phosphoric acid salt/fluorochemical, polyethylene phosphoric acid (PVPA), vincofos acid copolymer or water-soluble diazo resin.
The back side of carrier (promptly relative with bottom and imageable layer face) can be coated with antistatic agent and/or increase sliding layer or cover processing and " sense of touch " of flaggy (matte layer) to improve imageable element.
Utilize the imageable element of ir radiation imaging to generally include infrared absorbing agents, it is commonly called optical-thermal conversion material.The optical-thermal conversion material absorbing radiation also converts thereof into heat.Although optical-thermal conversion material is for optional with the hot body imaging, the imageable element that contains optical-thermal conversion material also can utilize the hot body imaging, for example thermal head or thermal head array.
Optical-thermal conversion material can be can absorbing radiation and convert thereof into any material of heat.Suitable material comprises dyestuff and pigment.Suitable pigment for example comprises, carbon black, phthalocyanine green, ferric oxide (III), manganese oxide, Prussian blue and prussian blue.Because carbon black has low cost and wide absorption band, makes it can be used in the image device with wide region peak emission wavelength, thereby be a kind of pigment that especially is suitable for.The size of granules of pigments should be not more than the layer thickness that contains this pigment.Preferably, the particulate size should be layer thickness half or littler.
In order to prevent that photographic developer from by insoluble material greasy filthization, preferably dissolving in the optical-thermal conversion material in this photographic developer.Optical-thermal conversion material can be the dyestuff with suitable absorption spectrum and solubleness.Dyestuff, especially having 750nm is preferred to the dyestuff of the high extinction coefficient of 1200nm.The example of suitable dye comprises the dyestuff of following kind: methyne, polymethine, the aryl methyne, cyanine, half cyanine, the chain cyanine, side's sour cyanines (squarylium), pyridine (pyrylium), oxonol, naphthoquinones, anthraquinone, porphyrin, azo, croconium, triarylamine, thiazole, indoline, azoles quinoline, indoles green grass or young crops, indotricarbocyanine, oxatricarbocyanine, phthalocyanine, sulphur flower cyanogen (thiocyanine), sulphur three carbonyl cyanines, merocyanine, cryptocyanine, the naphthalene phthalocyanine, polyaniline, polypyrrole, Polythiophene, chalcogenopyryloarylidene and bis (chalcogenopyrylo) polymethine, oxygen indolizine (oxyindolizine), pyrazoline azo and piperazine class.Absorbing dye all has disclosed in many publications, for example, and the EP 0823327 of Nagasaka, the U.S. Patent No. 4973572 of DeBoer, the U.S. Patent No. 5244771 of Jandrue, the United States Patent (USP) 5208135 of Patel, and the U.S. Patent No. 5401618 of Chapman.Other practical absorbing dye example comprises: ADS-830A and ADS-1064 (American Dye Source, Montreal, Canada), EC2117 (FEW, Wolfen, Germany), CyasorbIR 99 and Cyasorb IR 165 (Glendale Protective Technology), EpoliteIV-62B and Epolite III-178 (Epoline), SpectralR 830A and SpectralR840A (Spectra Colors) and IR dyestuff A and IR dyestuff B, its structure is as shown below:
IR dyestuff A
IR dyestuff B
The amount that is present in the optical-thermal conversion material in the element enough provide usually under the imaging wavelength at least 0.05 optical density(OD), preferably approximately 0.5 to about at least 2 to 3 optical density(OD).As those skilled in the known, the amount that produces the required compound of specific light density under specific wavelength can utilize the Beer law to determine.
In order to prevent to dissolve in the ir radiation imaging process, when element was multi-layer imageable element, imageable layer did not preferably have optical-thermal conversion material basically.That is to say, the optical-thermal conversion material in the imageable layer, if any, can absorb image-forming radiation, preferably less than about 3% image-forming radiation, and by imageable layer less than about 10%, if any, the quantity not sufficient of the image-forming radiation that is absorbed is to cause dissolving of imageable layer.
Imageable element of the present invention especially comprises the imageable element of the carbonic ether that contains the alkali soluble multipolymer, does not need the acidogenic agent of thermal activation.But comprise the image forming composition of carbonic ether of the acidogenic agent that contains polymkeric substance and thermal activation and each layer for example,
Photoreactive Polymers: The Science and Technology of Resists, A.Reiser, Wiley, New York, 1989, have disclosed among the pp.279-283.In these systems, acidogenic agent produces acid in the imaging process, but the carbonate functionalities in its catalytic elimination polymkeric substance changes the dissolution rate of imageable layer in alkaline developer.
The acidogenic agent of thermal activation is the compound that can be decomposed to form Br nsted acid by thermal initiation.The non-ionic type acidogenic agent for example comprises, the s-triazines that alkylhalide group replaces, and it is described in the U.S. Patent No. 3779778 of for example Smith to some extent.The s-triazines that alkylhalide group replaces is with one to three CX
3The s-triazines that group replaces, wherein X be bromine or, preferred chlorine.Example comprises 2-phenyl-4, two (the trichloromethyl)-s-triazines of 6-, 2,4,6-three (trichloromethyl)-s-triazine, 2-methyl-4, two (the trichloromethyl)-s-triazines of 6-, 2-styryl-4, two (the trichloromethyl)-s-triazines of 6-, 2-(to methoxyl-styrene)-4, two (the trichloromethyl)-s-triazines of 6-, 2-(4-methoxyl group-naphthyl-1-yl)-4,6-pair-trichloromethyl-s-triazine, 2-(4-oxyethyl group-naphthyl-1-yl)-4,6-pair-trichloromethyl-s-triazine, and 2-[4-(2-ethoxyethyl group)-naphthyl-1-yl]-4,6-pair-trichloromethyl-s-triazine.The ionic acidogenic agent for example comprises, salt, wherein the positively charged ion is iodine , sulphur , phosphorus , oxysulphoxonium, oxygen sulphur , sulfoxide (sulphoxonium), ammonium or diazonium, and negatively charged ion is chlorion, bromide anion or non-nucleophilic negatively charged ion such as tetrafluoroborate, hexafluoro-phosphate radical, hexafluoroarsenate root, hexafluoroantimonic anion, trifluoromethanesulfonic acid root, four (five fluoro-phenyl) borate, pentafluoroethyl group sulfonate radical, to methyl-benzyl sulfonate radical, ethylsulfonic acid root, trifluoromethyl acetate and pentafluoroethyl group acetate.Typical salt for example comprises, phenylbenzene iodine chloride , phenylbenzene iodonium hexafluorophosphate , phenylbenzene hexafluoro-iodide antimonate , 4,4 '-diisopropylbenzyl iodine chloride , 4,4 '-diisopropylbenzyl iodonium hexafluorophosphate , N-methoxyl group-α-Jia Jibiding -to the sulfonate of toluene, the a tetrafluoro borate of 4-p-methoxy-phenyl-diazonium, 4,4 '-two-dodecylphenyl iodine -hexafluorophosphate, 2-cyanoethyl-triphenyl phosphorus chloride , two-[4-phenylbenzene sulfonium base phenyl] sulfuration-two-hexafluorophosphate, two-4-dodecylphenyl hexafluoro-iodide antimonate , hexafluoro-antimonic acid triphenyl sulphur , Tetrafluoroboric acid triphenyl sulphur , the hexafluorophosphate of 2-methoxyl group-4-aminophenyl diazonium , hexafluoro-antimonic acid Phenoxyphenyl diazonium salt, and hexafluoro-antimonic acid anilino phenyl diazonium salt.
Yet, in imageable element of the present invention, comprise that especially in the imageable element of the carbonic ether that contains the alkali soluble multipolymer, imaging process does not need the acidogenic agent of thermal activation.Therefore, imageable element of the present invention, the imageable element that especially comprises the carbonic ether that contains the alkali soluble multipolymer do not comprise the acidogenic agent of thermal activation, and this illustrates in front.
But single-layer element comprises the image forming composition layer on the base material, and it is called as top layer or imageable layer.This imageable layer becomes after the heat exposure and dissolves in maybe and can be scattered in the photographic developer.But the single-layer element of thermal imaging is in the U.S. Patent No. 6090532 of for example West, the U.S. Patent No. 6280899 of Parsons, and the U.S. Patent Publication No.2002/0136961 of McCullough, and have disclosed among the WO99/21715.But image forming composition comprises that oil suction China ink polymer materials is a tackiness agent, dissolution inhibitor, optical-thermal conversion material, and above-mentioned alkali soluble multipolymer, or the mixture of above-mentioned alkali soluble multipolymer.Can be instead, perhaps additionally, polymeric material can comprise polar group and play the effect of tackiness agent and dissolution inhibitor simultaneously.Also can there be other material as the conventional component of imageable layer of individual layer imageable element.
Tackiness agent in the imageable layer will be called as first tackiness agent.Preferably, the tackiness agent in the individual layer imageable element is the film forming resol that a kind of light is stable, water insoluble, dissolve in photographic developer.Resol has a plurality of phenolic hydroxyl group groups, or on main polymer chain, or on side chain.Practical resol comprises the polyvinyl compound with phenolic hydroxyl group, polycarboxylated styrene and contain the multipolymer of hydroxy styrenes repeating unit for example, and the polymkeric substance and the multipolymer that contain the hydroxy styrenes repeating unit of replacement.Novolac resin, resol and polycarboxylated styrene are preferred resol.Novolac resin is more preferred.
Novolac resin is can buy on the market, and is known for a person skilled in the art.Usually the condensation reaction by phenol such as phenol, m-cresol, Ortho Cresol, p-cresol etc. and aldehyde such as formaldehyde, Paraformaldehyde 96, acetaldehyde etc. or ketone such as acetone prepares under the situation that acid catalyst exists.Typical novolac resin for example comprises phenol-formaldehyde resin, toluene resinox, phenol-toluene resinox, p-tert-butylphenol-formaldehyde resin and pyrogallol-acetone resin.Especially mixture or the phenol of the novolac resin of Shi Yonging by m-cresol, m-cresol and p-cresol under normal condition, make with formaldehyde reaction.
Imageable layer preferably includes dissolution inhibitor, and its solubility as first tackiness agent suppresses composition.Dissolution inhibitor has the polar functionalities group, and it comprises the atom with high electron density, is preferably selected from electronegative first row element, especially carbon, nitrogen and oxygen.Preferably dissolve in the dissolution inhibitor of photographic developer.
The practical polar group of dissolution inhibitor for example comprises, azo group, diazonium groups, ketone group, sulfonate ester group, bound phosphate groups, triarylmethane group, group, for example sulphur , iodine and phosphorus ; The group that comprises nitrogen-atoms in the heterocycle; And the group that contains the nitrogen-atoms (normally quaternized nitrogen-atoms, i.e. ammonium) of positively charged atom, especially positively charged.Can be used as dissolution inhibitor, the compound of (promptly quaternized) nitrogen-atoms that contains positively charged for example comprises that tetraalkyl ammonium compound, and quaternized heterogeneous ring compound are as quinoline compound, benzothiazole compound, pyridine compounds and imidazolium compounds.Also can use the compound that contains other polar group, the compound that for example contains ether, amine, azo, nitro, ferrocene, sulfoxide, sulfone and two sulfones is as dissolution inhibitor.Dissolution inhibitor can be for comprising the monomeric compound and/or the polymkeric substance of adjacent diazo naphthoquinone part.
Preferred dissolution inhibitor group is a triarylmethane dye, for example ethyl violet, Viola crystallina, Victoria Green WPB, bright green, victoria blue B, victoria blue, victoria blue BO, BASONYL Violet 610 and D11 (PCAS, Longjumeau, France).These compounds can also be used as contrast dye, and it makes not imaging region and imaging region differentiation to some extent in the imageable element that develops.
Selectively, perhaps additionally, first tackiness agent can comprise polar group, and it is used as the acceptor site of the hydroxyl generation bonding that exists in hydrogen and this first tackiness agent, and thereby simultaneously as first tackiness agent and dissolution inhibitor.The derivatize level enough height so that polymeric material as dissolution inhibitor, but can not be too high so that after the thermal imaging first tackiness agent be insoluble in the photographic developer.Although required derivatize degree depends on the character of first tackiness agent and the character of introducing the part that contains polar group of polymer materials, about 0.5mol% that derives usually is to about 5mol%, and preferably approximately 1mol% is to the hydroxyl of about 3mol%.With having the compound derivatives resol that contains the diazo naphthoquinone part is known, and describes to some extent in the U.S. Patent No. 5705308 and 5705322 of for example West.
Comprise polar group and play one group of tackiness agent of dissolution inhibitor effect the novolac polymer material that is derivatize, wherein the part phenolic hydroxyl group has been converted to sulphonate, preferred phenylbenzimidazole sulfonic acid ester class or p-toluenesulfonic esters class.By under the situation that has alkali such as tertiary amine, polymeric material and for example SULPHURYL CHLORIDE such as Tosyl chloride and/or can realize the derivatize process with the reaction of above-mentioned any other SULPHURYL CHLORIDE.Practical material has novolac resin, and wherein approximately 1mol is to 3mol%, and preferably approximately 1.5mol% has been converted to phenylbenzimidazole sulfonic acid ester or p-toluenesulfonic esters (tolylsulfonyl) group to the hydroxyl of about 2.5mol%.
But the image forming composition of individual layer imageable element and imageable layer can also comprise other composition, but the dyestuff and the tensio-active agent of the image forming composition component of for example conduct routine.Tensio-active agent for example can be used as coating supporting agents and exists.Exist dyestuff to help the visual inspection of imaging and/or developing element.The printout dyestuff makes imaging region and imaging region not distinguish to some extent in treating processes.Do not distinguish to some extent by imaging region and imaging region in the imageable element that develops for contrast dye.Preferably, described dyestuff does not absorb image-forming radiation.Triarylmethane dye as mentioned above, also can be used as contrast dye.
In the individual layer imageable element, imageable layer comprises typically that based on the about 40wt% of this layer dry weight to about 90wt%, preferably approximately 55wt% is to first tackiness agent of 75wt% or the mixture of first tackiness agent; To about 30wt%, preferably approximately 1wt% is to the dissolution inhibitor of 15wt% or the mixture of dissolution inhibitor based on the about 0.5wt% of this layer dry weight; To about 20wt%, preferably approximately 1wt% is to the optical-thermal conversion material of 10wt% based on imageable layer dry weight 0.5wt%; To about 30wt%, preferably approximately 5wt% is to the alkali soluble multipolymer of 20wt% or the mixture of alkali soluble multipolymer based on the about 3wt% of imageable layer dry weight.
Sandwich type element includes top layer or imageable layer on bottom.Also can there be other each layer, for example absorber layer and/or blocking layer.When having bottom, the mixture of alkali soluble multipolymer or alkali soluble multipolymer is in this bottom.
But the conventional any imageable layer that uses all can be used in this multi-layer imageable element in the thermal imaging element that multilayer, eurymeric, alkalescence can be developed.These elements are in U.S. Patent No. 6294311, U.S. Patent No. 6352812 and the U.S. Patent No. 6593055 of for example Shimazu, the U.S. Patent No. 6352811 of Patel, the U.S. Patent No. 6358669 of Hauck, the U.S. Patent No. 6528228 of Savariar-Hauck, and have disclosed in the United States Patent (USP) 6858359 of Kitson.
The imageable layer of multi-layer imageable element is positioned at the bottom top.It dissolves in maybe and can be scattered in the photographic developer after the heat exposure.This imageable layer is similar to the imageable layer of individual layer imageable element recited above usually, does not have the mixture of alkali soluble multipolymer or alkali soluble multipolymer only usually.It generally includes the polymeric material (being called as tackiness agent) and the dissolution inhibitor of oil suction China ink.Selectively, perhaps additionally, this polymeric material comprises polar group and plays a part tackiness agent and dissolution inhibitor simultaneously.
The dissolution inhibitor that is used for the imageable layer of multi-layer imageable element is illustrated in the above.This imageable layer also comprises other composition as the conventional component of imageable layer of multi-layer imageable element.These compositions for example comprise, tensio-active agent and dyestuff, as mentioned above.
The tackiness agent that is used for the imageable layer of multi-layer imageable element is the film forming resol that light is stable, water insoluble, dissolve in photographic developer, first tackiness agent for example recited above.In some cases, may wish to comprise novolac resin in imageable layer, it has the highest weight average molecular weight that remains on the solubleness in common coating solvent such as acetone, tetrahydrofuran (THF) and the 1-methoxy Virahol.Can use the imageable layer that comprises novolac resin, it comprises novolac resin that m-cresol is for example only arranged (promptly contain at least approximately 97mol% m-cresol those) and has nearly 10mol% p-cresol, weight average molecular weight is m-cresol/p-cresol novolac resin of about 10000 to about at least 25000.Can also use and comprise that weight average molecular weight is about 8000 to about 25000 the imageable layer of the m-cresol of 10mol% p-cresol/p-cresol novolac resin at least that contains.Novolac resin by the solvent condensation prepared is desirable in some cases.The imageable layer that comprises these resins has disclosed in the United States Patent (USP) 6858359 of Kitson.
Bottom is between the water-wetted surface and imageable layer of base material.After imaging, in imaging region, it is come along together with imageable layer and remove, thereby expose the bottom water-wetted surface of base material with photographic developer.The polymeric material that will be called as second tackiness agent in bottom preferably dissolves in the photographic developer to prevent photographic developer greasy filthization.In addition, it preferably dissolves in the solvent that is used for covering imageable layer, can not dissolve bottom so that imageable layer can cover on the bottom.
Be suitable for the polymeric material of making second tackiness agent and comprise those that contain acid and/or phenol functional group, and this class mixtures of material.The polymeric material of particularly suitable is maleimide, the especially N-phenylmaleimide that comprises that N-replaces, the polyvinyl alcohol acetal, the methacrylic acid amides, especially methacrylic acid acid amides, and vinylformic acid and/or methacrylic acid, especially methacrylic acid, multipolymer.More preferably, there are two functional groups in the polymeric material, most preferably, have whole three functional groups in this polymeric material.Such preferred polymer materials is the multipolymer of N-phenylmaleimide, methacrylic acid acid amides and methacrylic acid, more preferably contain about 25 to about 75mol%, the N-phenyl maleoyl acid imide of preferably approximately 35 to about 60mol% with polymer form; About 10 to about 50mol%, preferably approximately 15 is to about 40mol% methacrylic acid acid amides; And about 5 to about 30mol%, those of the methacrylic acid of preferably approximately 10 to about 30mol%.Other hydrophilic monomer, for example hydroxyethyl meth acrylate can be used for replacing some or all of methacrylic acid acid amides.Other alkali soluble monomer, for example vinylformic acid can be used for replacing some or all of methacrylic acids.
These polymeric materials dissolve in the alkaline photographic developer.In addition, they dissolve in the mixture of methyl lactate/methyl alcohol/dioxolane (15: 42.5: 42.5 wt%), and this mixture can be used as the coating solvent of bottom.Yet they are insoluble in the solvent of acetone and so on, and it can be used as the solvent of coating imageable layer on bottom and can not dissolve bottom.
Bottom can also comprise resin or have the activation methylol and/or the resin of activation alkylation methylol.This resin comprises, for example: resol and alkylation analogue thereof; Melamine methylol resin and alkylation analogue, for example melamine formaldehyde resin; Methylol glycoluril resin and alkylation analogue, for example glycoluril-formaldehyde resin; Thiocarbamide-formaldehyde resin; Guanamines-formaldehyde resin; And benzo melamine formaldehyde resin.Commercially available melamine formaldehyde resin and glycoluril-formaldehyde resin comprise, for example CYMEL resin (DynoCyanamid) and NIKALAC resin (Sanwa Chemical).
One or more resins with activation methylol and/or activation alkylation methylol are preferably the mixture of resol or resol.Resol is known for a person skilled in the art.They utilize excessive phenol, the prepared in reaction under alkaline condition by phenol and aldehyde.Commercially available resol for example comprises, GP649D99 resol (Georgia Pacific) and BKS-5928 resol (UnionCarbide).
It is that about 50wt% arrives about 75wt% that bottom typically comprises based on the bottom dry weight, and preferably approximately 55wt% is to second tackiness agent of about 70wt% or the mixture of second tackiness agent; When existing, be that about 5wt% arrives about 20wt% based on the bottom dry weight, preferably approximately 7wt% has the resin or the resin compound of activation methylol and/or activation alkylation methylol to about 15wt%; Based on the bottom dry weight is that about 5wt% arrives about 25wt%, and preferably approximately 10wt% is to the optical-thermal conversion material of 20wt%; And be about 3wt% to about 30wt% based on the bottom dry weight, preferably approximately 5wt% is to the alkali soluble multipolymer of about 20wt% or the mixture of alkali soluble multipolymer.
The bottom of multi-layer imageable element generally includes optical-thermal conversion material.Perhaps, this optothermal material can be in imageable layer or in independent absorber layer.
When having absorber layer, it is between imageable layer and base material.When also having bottom, absorber layer is between imageable layer and bottom.Absorber layer is preferred mainly to be made of optical-thermal conversion material and optional tensio-active agent.If it is present in the independent absorber layer rather than it can use less optical-thermal conversion material in bottom and/or imageable layer.When having absorber layer, imageable layer does not preferably have optical-thermal conversion material basically, and promptly imageable layer does not preferably absorb the radiation that is used for imaging, and normally 800nm is to the interior radiation of 1200nm scope.The absorber layer preferred thickness is enough to absorb at least 90%, preferred at least 99% image-forming radiation.Usually, the coating wt of absorber layer is about 0.02g/m
2To about 2g/m
2, preferably approximately 0.05g/m
2To about 1.5g/m
2The element that comprises absorber layer discloses in the U.S. Patent No. 6593055 of Shimazu.
In order to make optical-thermal conversion material in the manufacturing of imageable element with deposit in the process minimumly to the migration of imageable layer from bottom, this element can comprise a blocking layer between bottom and imageable layer.The blocking layer comprises the polymeric material that dissolves in the photographic developer.If this polymeric material is different from the polymeric material in the bottom, then it preferably dissolves in polymer materials in the bottom and is insoluble in wherein at least a organic solvent.The preferred polymer materials on blocking layer is a polyvinyl alcohol.When the polymeric material in the blocking layer was different from polymeric material in the bottom, what this blocking layer should be less than underlayer thickness was about 1/5th, preferably less than 1/10th of underlayer thickness.
The individual layer imageable element can utilize routine techniques, as coating or laminating, by described imageable layer is applied to prepare on the base material.Typically, described each composition is dissolved in the suitable coating solvent, and the mixture that obtains is passed through ordinary method, for example spin coating, blade coating, gravure formula apply, mouthful pattern is coated with or rolling method is coated on the water-wetted surface of base material.
The preparation multi-layer imageable element can sequentially be applied to bottom on the base material water-wetted surface; If present, absorber layer or blocking layer are applied on the bottom, utilize routine techniques to apply imageable layer then.Typically, described each composition is dispersed or dissolved in the suitable coating solvent, and with the mixture that obtains for example spin coating of method, bar coating, the gravure formula by routine apply, mouthful pattern coating or rolling method be coated with.Bottom can be by for example, the mixture of methylethylketone, 1-methoxy Virahol, butyrolactone and water; The mixture of metacetone, water, methyl lactate and butyrolactone, and the mixture of metacetone, water and methyl lactate is used.
When neither existing the blocking layer also not have absorber layer, imageable layer is coated on the bottom.In order to prevent the bottom dissolving and mix that imageable layer should be coated with by the solvent that bottom is insoluble to wherein basically with imageable layer.Thereby the coating solvent that is used for imageable layer should be each composition sufficiently soluble of imageable layer in wherein being insoluble to wherein solvent basically so that can make imageable layer and any bottom.Typically, to be used to be coated with the solvent polarity of imageable layer bigger for the solvent ratio that is used for barrier coating.Imageable layer can be used by the mixture of for example metacetone or metacetone and 1-methoxyl group-2-propyl-acetic acid ester.Be coated with the middle drying step that is used for the decoating solvent before the imageable layer in the above, promptly the step of dry bottom if any, also can be used to prevent each layer mixing.
Perhaps, the two-layer extrusion coated method that can be by routine of bottom, imageable layer or this is applied by the molten mixture of each component of layer.Typically, this molten mixture does not contain volatile organic solvent.
Element can utilize laser or laser array to carry out thermal imaging, and described laser or laser array are emitted near infrared or the ir radiation of regulating in the wavelength region may of described imageable element absorption.Usually use ir radiation, especially carry out imaging to the ir radiation in about 1200nm scope at about 800nm.Imaging utilizes at about 830nm usually, approximately the luminous laser apparatus of 1056nm or about 1064nm place is realized.Suitable commercial imaging device comprises picture regulator such as CREO Trendsetter (Creo, Burnaby, British Columbia, Canada), Screen PlateRite 4300 types, 8600 types and 8800 types (Screen, Rolling Meadows, Chicago, Ilinois, USA), and Gerber Crescent 42T (Gerber).
Perhaps, imageable element can utilize hot body, carries out thermal imaging as the equipment that contains thermal printing head of routine.Suitable equipment comprises at least one thermal head, but generally include the thermal head array, the TDK Model No.LV5416 that for example is used for hot facsimile recorder and sublimation printer, GS618-400 thermal plotter (Oyo Instruments, Houston, TX, USA), perhaps Model VP-3500 thermal printer (Seikosha America, Mahwah, NJ, USA).
Imaging process generates image-forming component, and it comprises not imaging area of the latent image of imaging area and complementation.Image-forming component develops and forms printing plate, or print format, exposes the water-wetted surface of bottom substrate and sub-image is transformed into image by removing imaging region.
Suitable photographic developer depends on the solubility feature of each composition that exists in the imageable element.Photographic developer can be can see through and remove the imaging area of imageable element but do not influence the complementary not any liquid or the solution of imaging area basically.Although be not subjected to the constraint of any theory or explanation, it is believed that pattern recognition is based on kinetic effect.The imaging area of imageable layer is removed rapidlyer than imaging region not in photographic developer.Carry out enough developing for a long time with other one or more layers the bottom zone of the imaging area of removing imageable layer and this element, but not too long and removed the not imaging area of this imageable layer.Therefore, imageable layer " can not be removed " or " insoluble " concerning photographic developer before being said to be in imaging, and to be said to be to be " soluble " or " removable " to photographic developer in the imaging zone, because it is removed than imaging region not in photographic developer, promptly dissolve and/or disperse rapidlyer.Typically, bottom is dissolved in the photographic developer and imageable layer dissolving and/or be scattered in the photographic developer.
Can use the photographic developer of high pH.It is about 11 that the common pH of high pH developer is at least, and is more typically approximately at least 12, even is more typically about 12 to about 14.High pH developer also generally includes at least a alkalimetal silicate, and for example lithium silicate, water glass and/or potassium silicate do not have organic solvent usually basically.Utilize oxyhydroxide or alkalimetal silicate or mixture that alkalescence can be provided.Preferred oxyhydroxide is the oxyhydroxide of ammonium, sodium, lithium and particularly potassium.Alkalimetal silicate has and is at least 0.3 SiO
2With M
2The weight ratio of O (wherein M is a basic metal), preferably this ratio is, 0.3 to 1.2, more preferably 0.6 to 1.1, most preferably be 0.7 to 1.0.The amount of alkalimetal silicate is every 100g composition 20gSiO at least in the photographic developer
2, be preferably 20 to 80g, most preferably be 40 to 65g.High pH developer can be used in the submergence treater.Typical high pH developer comprises PC9000, PC3000, Goldstar
TM, Greenstar
TM, ThermalPro
TM, PROTHERM , MX1813 and MX1710, alkaline aqueous solution photographic developer, all can be available from Kodak Polychrome Graphics LLC.Another kind of useful photographic developer contains 200 parts of Goldstar
TMPhotographic developer, 1499,1 parts of metal metasilicate sodium of 4 parts of polyoxyethylene glycol (PEG) pentahydrate, and 0.5 part of TRION H-22 tensio-active agent (phosphate ester surfactants).
After the development, the printing plate that the water flushing obtains is also dry.Drying process can be implemented by ir emitter or warm air routinely.After the drying, can be with printing plate with comprising one or more water-soluble polymerss, for example polyvinyl alcohol, polymethyl acrylic acid, polymethyl acrylic acid acid amides, poly-hydroxyethyl methacrylate, polyvinyl methyl ether, gelatin and polysaccharide are handled as dextrin, amylopectin, Mierocrystalline cellulose, Sudan Gum-arabic and alignic hydrosol.Preferable material is a Sudan Gum-arabic.
Plate after development and the gel is toasted to improve the print stroke of plate.Can be for example, about 220 ℃ to about 260 ℃ of bakings about 5 minutes to about 15 minutes down, perhaps about 110 ℃ to about 130 ℃ down baking about 25 arrive about 35 minutes.
Industrial applicibility
In case the lithographic printing plate precursor imaging and the formation planographic printing plate that develops just can be by being applied to enforcement printing on its surperficial image with wetting liquid and planography printing ink afterwards.Imaging region not, promptly the hydrophilic substrate surface that exposes by imaging and developing process absorbs wetting liquid; Imaging region, promptly the developing process zone of not removing absorbs printing ink.The hectograph that utilizes offset printing then directly or indirectly with ink transfer to suitable reception material (for example cloth, paper, metal, glass or plastics) so that the image impression of expection to be provided in the above.
Can see advantage of the present invention with reference to following examples, embodiment explains but unrestricted the present invention.
Embodiment
Unless otherwise noted, described per-cent is based on the total solid weight per-cent in the coating solution.
Nomenclature
The AIBN Diisopropyl azodicarboxylate (DuPont, Wilmington,
Delaware，USA)
Astro Mark III wetting liquid (Dainippon Ink and Chemical, Tokyo,
Japan)
BC 1-butyl cellosolve (Butyl CELLOSOLVE )
Viola crystallina C.I.42555, alkaline purple 3; λ
Max=588nm
[(p-(CH
3)
2C
6H
4)
3 +Cl]
BYK-307 polyethoxylated dimethyl polysiloxane multipolymer (BYK
Chemie，Wallingford，CT，USA)
CBS011 multipolymer, face structure (embodiment 9) as follows
The commercial forme film setter of using of CREO Trendsetter uses Procom Plus software also
3230 operations under the 830nm wavelength (Creo Products,
Burnaby，BC，Canada)
Copolymer 1 contains 41.5mol% N-phenylmaleimide, 21mol%
The copolymerization of methacrylic acid and 37.5% Methacrylamide
Thing
The DAA Pyranton
The DMF dimethyl formamide
ELECTRA thermo-sensitivity, eurymeric, individual layer, adjusting, that inhibition contains phenolic aldehyde is clear
Lithographic printing plate precursor (the Kodak Polychrome of EXCEL lacquer
Graphics Norwalk，CT，USA)
Ethyl violet C.I.42600; CAS 2390-59-2 (λ
Max=596nm)
[(p-(CH
3CH
2)
2NC
6H
4)
3C
+Cl](Aldrich，
Milwaukee，WI，USA)
EUV-5 contains the 5wt%N-phenyl maleimide; The 10wt% methacrylic
Acid amides; The 48wt% vinyl cyanide; 31wt%
H
2C＝C(CH
3)-CO
2-CH
2CH
2-NH-CO-NH-p-
C
6H
4-OH; And 6wt%H
2C=C (CH
3)-CO
2-NH-p-
C
6H
4The multipolymer of-OH
Goldstar
TMPhotographic developer is based on the alkaline aqueous solution photographic developer (Kodak of metal metasilicate sodium
Polychrome Graphics，Norwalk，CT，USA)
The GP649D99 resol (Georgia-Pacific, Atlanta,
GA，USA)
IR dyestuff A infrared absorbing dye (λ
Max=830nm) (Eastman
Kodak, Rochester, NY USA) (sees top knot
The structure formula)
IR dyestuff C 2-[2[2-chloro-3-[(1,3-dihydro-1,3,3-trimethylammonium-2H-indoles-
The 2-subunit) ethylidene]-1-tetrahydrobenzene-1-yl] vinyl]-
1,3,3-trimethylammonium-3H-iodo indoles bromide
(Honeywell Specialty Chemicals，
Morristown，NJ，USA)
Staggered polyethylene enamelled paper No.22; 6g/m
2(Thilmany,
Kaukauna，WI，USA)
The carton paper natural colored, unglazed kraft paper 90g/m
2, coat mat black
Look new LDPE (film grade) 20g/m
2(Thilmany,
Kaukauna，WI，USA)
Novolac resin (the Rutgers-Plenco of LB6564 phenol/cresylol
LLC，Sheboygan，WI，USA)
The N-13 novolac resin; 100% m-cresol; MW 13000
(Eastman Kodak Rochester，NY，USA)
RAR-62 contains the 5wt%N-phenyl maleimide; The 10wt% methacrylic
Acid amides; 45% vinyl cyanide; 40wt% H
2C=C (CH
3)-
CO
2-CH
2CH
2-NH-CO-NH-p-C
6H
4The copolymerization of-OH
Thing
SILIKOPHEN phenmethyl polyorganosiloxane resin (Tego Chemie Service,
P50X Essen，Germany)
0.3 millimeter specification of base material A is passed through electrolysis granulation, anodizing, is also used
Aluminium flake after the inorganic phosphate solution-treated
M-TMI 1-(1-isocyanic acid-1-methyl)-ethyl-3-(1-methyl)-ethene
Base benzene
The TN-13 N-13 novolac resin of Tosyl chloride functionalization
Embodiment 1
This embodiment has represented the preparation of the t-BOC derivative (t-BOC RAR-62) of RAR-62.RAR-62 (29.95g), dioxolane (135.8g) and DMF (40g) are dissolved in the flask.The time of following with 30 minutes adds di-t-butyl sodium bicarbonate (10.00g), salt of wormwood (6.50g) and 18-crown-6 (2.0g).Mixture was at room temperature stirred two hours.By being deposited in the water and separated product (37.5g, output 98.2%) and 50 ℃ dry 2 days down.
IR: from t-BOC, 3367cm
-1(s) NH, 1810 ﹠amp; 1758cm
-1(s) C=O, 1670cm
-1(s) N-CO-N, 1119 ﹠amp; 1069cm
-1(s) C=O stretches, 845cm
-1(s)-and O-C (O)-O-, 576cm
-1(m) CN.
1H NMR (DMSO-d
6In): δ 1.40 (9H, m).δ does not observe peak value in 8.20 places.By contrast, RAR-62 have at δ 8.20 places peak value (1H, s).
Embodiment 2
This embodiment has represented t-BOC derivative (t-BOC EUV-5) synthetic of EUV-5.EUV-5 (29.95g), dioxolane (135.8g) and DMF (40g) are dissolved in the flask.The time of following with 30 minutes adds di-t-butyl sodium bicarbonate (10.00g), salt of wormwood (6.50g) and 18-crown-6 (2.0g).Mixture was at room temperature stirred two hours.By being deposited in the water and separated product (37.4g, output 97.9%) and 50 ℃ dry 2 days down.IR: from t-BOC, 3373cm
-1(s) NH, 1812 ﹠amp; 1760cm
-1(s) C=O, 1670cm
-1(s) N-CO-N, 1119 ﹠amp; 1070cm
-1(s) C=O stretches, 845cm
-1(s)-and O-C (O)-O-, 576cm
-1(m) CN.
1H NMR (DMSO-d
6In): δ 1.40 (9H, m).δ does not observe peak value in 8.20 places.By contrast, EUV-5 have at δ 8.20 places peak value (1H, s).
Embodiment 3 and 4 and comparative example 1 and 2
This embodiment has represented the individual layer imageable element.By the material dissolves in the table 1 is prepared into coating solution in 2-butanone/1-methoxyl group-Virahol/butyrolactone/water in (65/15/10/10).Utilize the coiling rod that each coating solution is coated on the base material A.The imageable element that obtains is made of the imageable layer on the base material, with its Mathis Labdryer LTE stove (Werner Mathis, Switzerland) in 100 ℃ dry 90 seconds down.The dry weight of each imageable layer is 1.5g/m
2
Table 1
| The embodiment sequence number | ||||
| C1 | 3 | C2 | 4 | |
| Composition | Parts by weight | |||
| RAR-62 | 20 | - | - | - |
| t-BOC RAR-62 | - | 20 | - | - |
| EUV-5 | - | - | 20 | - |
| t-BOC EUV-5 | - | - | - | 20 |
| N-13 | 20 | 20 | 20 | 20 |
| LB6564 | 50.65 | 50.65 | 50.65 | 50.65 |
| Viola crystallina | 2 | 2 | 2 | 2 |
| IR dyestuff A | 2 | 2 | 2 | 2 |
| SILIKOPHEN P50X | 5 | 5 | 5 | 5 |
| BYK 307 | 0.35 | 0.35 | 0.35 | 0.35 |
Cover this imageable element is staggered, with the kraft paper parcel and to put into the baking oven with gas blower following 3 days in 55 ℃.With the imageable element after the thermal treatment that obtains with CREO Trendsetter 3244 (Creo Inc., Burnaby, British Columbia, Canada) internal test mode (icon 0) is 100,150 and 200mJ/cm
2The imaging energy density under imaging.Imageable element after the imaging is being contained Goldstar
TMThe Mercury Mark V treater of photographic developer (immerse treater, Kodak Polychrome Graphics, Norwalk, CT develops in USA), and under 23.5 ℃, processing speed is 500 and 1500mm/min.Estimate the removing value (imaging region is dissolved in the imaging exposure first time in the photographic developer fully) and the optimum resolution (imageable element provides the imaging energy of optimized image) of this imageable element.
Other imageable element with 50% lineament with 200mJ/cm
2Imaging is handled in Mercury treater as above then, and processing speed is 750mm/min.Imaging area segment with 50% and unexposed area (100% solid state image) were immersed in Astro Mark III wetting liquid/2-propanol/water (6/10/84) 8 hours and 24 hours.With image gently with the wiping of cotton pad with remove any decohere, in water after flushing and the drying, with D196 densometer (GretagMabcBeth, Regensdorf, Switzerland) reading.The result is as shown in table 2.
Table 2
| The minimum exposure that following result is required: | ||||
| Removing value (mJ/cm 2) | Optimum resolution (mJ/cm 2) | |||
| 500mm/min | 1500 mm/min | 500mm/min | 1500 mm/min | |
| C1 | No image | No image | No image | No image |
| 3 | ＜100 | ＜100 | 150 | 150 |
| C2 | No image | No image | No image | No image |
| 4 | ＜100 | ＜100 | 150 | 150 |
Table 2 (continuing)
| Immerse Astro/2-following time of propanol/water point size afterwards | ||||||
| 0 hour | 8 hours | 24 hours | ||||
| 50％ | 100％ | 50％ | 100％ | 50％ | 100％ | |
| C1 | 51 | 100 | 49 | 100 | 48 | 100 |
| 3 | 52 | 100 | 52 | 100 | 49 | 100 |
| C2 | 51 | 100 | 49 | 100 | 49 | 100 |
| 4 | 53 | 100 | 53 | 100 | 51 | 100 |
Table 2 (continuing)
The version that disappears test
| 210 ℃ of bakings down a | 230 ℃ of bakings down | |
| C1 | 2 | 1 |
| 3 | 2 | 1 |
| C2 | 5 | 2 |
| 4 | 5 | 1 |
a1=does not have imageable layer to be removed; The imaging layer of 5=50% is removed
Embodiment 5 and 6 and comparative example 3 and 4
This embodiment has represented multi-layer imageable element.
Bottom: be prepared into coating solution in 2-butanone/1-methoxyl group-Virahol/butyrolactone/water in (65/15/10/10) by the material dissolves that will list in the table 3.Utilize the coiling rod that each coating solution is coated on the base material A.The element that obtains is made of the bottom on the base material, and it is following dry 35 seconds at 135 ℃.The dry coating weight of bottom is 1.3g/m
2
Table 3
| The embodiment sequence number | ||||
| C3 | 5 | C4 | 6 | |
| Composition | Parts by weight | |||
| RAR-62 | 15 | - | - | - |
| t-BOC RAR- 62 | - | 15 | - | - |
| EUV-5 | - | - | 15 | - |
| t-BOC EUV-5 | - | - | - | 15 |
| Copolymer 1 | 59.65 | 59.65 | 59.65 | 59.65 |
| GP649D99 | 10 | 10 | 10 | 10 |
| IR dyestuff A | 15 | 15 | 15 | 15 |
| BYK 307 | 0.35 | 0.35 | 0.35 | 0.35 |
Imageable layer: will contain that (92: 8, w: the coating solution of the BYK-307 of the ethyl violet of functionalization novolac resin, 0.3 parts by weight of preparation and 0.35 parts by weight was applied on each bottom with the coiling rod among the embodiment 7 of 99.35 parts by weight w) at metacetone/acetate 1-methoxyl group propyl ester.Each imageable element that obtains is following dry 35 seconds at 135 ℃.Imageable layer dry coating weight be 0.9g/m
2
The imageable element that obtains is calculated in following test:
Removing value and optimum resolution: with internal test mode (icon 0) imageable element is carried out imaging with the radiation of 830nm, on CREO 3230 Trendsetter with 83,86,93,99,107,116,127 and 140mJ/cm
2Carry out with 9 watts laser energy.Then with the imageable element Goldstar of imaging
TMPhotographic developer carries out machine handling in Mercury Mark V treater (processing speed of 750mm/min, 23.5 ℃ photographic developer temperature).Estimate the removing value (imaging region is dissolved in the imaging exposure first time in the photographic developer fully) and the optimum resolution (imageable element provides the imaging energy of optimized image) of this imageable element.
Only test: under 22 ℃, drip Goldstar greatly one at the photographic developer drop on the bottom
TMPhotographic developer places on the bottom of each element, the record dissolving required time of this layer.
Test at the photographic developer drop on the complete imageable element: under 22 ℃, drip Goldstar greatly one
TMPhotographic developer places on each imageable element, the record dissolving required time of this layer.
Test at the solvent tolerance drop on the complete imageable element: under 22 ℃, dripped Pyranton/water (80: 20 greatly one, v: v) or 1-butyl cellosolve/water (80: 20, v: v) place on the imageable layer of each imageable element, the record dissolving required time of this layer, and estimate the quantity of material of removing after 1 minute.
Edition glue that disappears after the baking test: imageable element was toasted 8 minutes down in 210 ℃ and 230 ℃ in Mathis LTE Labdryer stove (Werner Mathis Switzerland, rotation speed of the fan 1000rpm).The Kodak Polychrome Graphics eurymeric that will the contain hydrofluoric acid then edition glue that disappears is applied to last 12 minute of imageable layer after the baking, estimate remaining imageable layer amount (1=does not have imageable layer to be removed, and the imageable layer of 5=50% is removed) after this.
The result is as shown in table 4.
Table 4
| Embodiment | Goldstar TMDrop test (second) | The minimum exposure that following result is required: | Solvent tolerance drop test (second) | |||
| Bottom | Complete element | Removing value (mJ/cm 2) | Optimum resolution (mJ/cm 2) | DAA/ water | BC/ water | |
| C3 | 10 | 180 | 116 | 127 | 210 | ＞300 |
| 5 | 14 | 210 | 107 | 116 | 180 | 300 |
| C4 | 12 | 210 | 127 | 127 | 300 | ＞300 |
| 6 | 16 | 210 | 116 | 127 | 270 | 300 |
Table 4 (continuing)
The version that disappears test
| 210 ℃ of bakings down a | 230 ℃ of bakings down | |
| C3 | 1 | 1 |
| 5 | 2 | 2 |
| C4 | 2 | 1 |
| 6 | 3 | 2 |
a1=does not have imageable layer to be removed; The imageable layer of 5=50% is removed
Embodiment 7
This embodiment has represented the preparation method with Tosyl chloride functionalization novolac resin.N-13 (24g, 199.75 millis rub) is stirred in the adding acetone (66g), the mixture that obtains is cooled to 10 ℃ in ice/water-bath.Time with 1min under 10 ℃ adds Tosyl chloride (20.02 millis rub).Time with 2min under 10 ℃ adds triethylamine (19.63 millis rub).Reaction mixture is being lower than 15 ℃ of stirring 10min down.Added acetic acid (8.33 millis rub) with 10 second time under 10 ℃, and reaction mixture is stirred 15min.Under 15 ℃, add entry/ice (160g) and acetic acid (1.2g, 20.02 millis rub) and reaction mixture is being stirred 5min below 15 ℃ with time of several minutes.
Supernatant liquor is inclined from the viscous solid that is formed at the reaction flask bottom.Add acetone (354g), and stirred reaction mixture is up to obtaining clear soln.Add entry/ice (160g) and acetic acid (1.2g, 20.02 millis rub) and at stirred reaction mixture 5min below 15 ℃ with several minutes times.Add acetone (354g) again from the viscous solid supernatant liquor that inclines, and stirred reaction mixture is up to obtaining clear soln.Acetone soln with 25% adds in the mixture of ice (460g), water (460g) and acetic acid (0.5g).The mixture that obtains was stirred 20 minutes, throw out is settled down and incline supernatant liquor.Repeat this process with remaining acetone soln.Merge moist polymkeric substance and draw branch, water (460g) washed twice is also dry.Output: 88%.
Embodiment 8
This embodiment has represented the preparation copolymer 1, promptly contains the multipolymer of 41.5mol%N-phenyl maleimide, 21mol% methacrylic acid and 37.5% Methacrylamide.With N-phenyl maleimide (23.59g), methacrylic acid (5.93g), Methacrylamide (10.48g) and dioxolane/ethanol (50: 50 (v: v); 126.01g) place the 1L reactor that reflux exchanger, nitrogen supply, thermometer, agitator and heating mantles are housed.Nitrogen was passed through the reaction mixture bubbling one hour.Reacting by heating to 60 ℃ and add 2,2-Diisopropyl azodicarboxylate (AIBN) (0.054g in 10g dioxolane/ethanol) under nitrogen.
Reaction mixture is stirred about 20hr down in 60 ℃ under nitrogen.Reaction mixture is slowly added (approximately 1L) in the entry, filter the precipitation that obtains.Contain 80: 20 ethanol/water washing precipitates of about 5 concentrated hydrochloric acids with about 1L, filter once more,, filter once more, 50 ℃ of dryings two days down with about 1L ethanol/water washing in 80: 20.Output: 80%.
Embodiment 9
This embodiment has represented the preparation of multipolymer of the present invention.
The monomer preparation
50.23g m-TMI is packed in the four neck flasks of 500ml, and this flask is equipped with heating mantles, temperature regulator, mechanical stirrer, condenser and nitrogen inlet.Under nitrogen atmosphere, reaction mixture is heated to 30 ℃.Mixture with 234.2g N,N-DIMETHYLACETAMIDE and 27.82g p-aminophenol adds down at 30 ℃ then.Slow elevated temperature to 40 ℃ after two hours.By at 2275cm
-1The disappearance that the NCO at place absorbs comes the monitoring reaction process.
The preparation of CBSS011
In the 1L reactor that Liebig condenser, nitrogen supply, thermometer, agitator, heating mantles are housed, the monomer (16.00g) that under nitrogen, prepares in heating N-phenyl maleimide (2.00g), vinyl cyanide (18.00g), Methacrylamide (4.00g), the preceding step and dioxolane/ethanol (the mixture 1hr of 50: 50 (v: v) 126.01g).Will the AIBN (0.054g) in dioxolane/ethanol (10g) add in the reaction mixture and under 60 ℃ under nitrogen the about 20hr of continuously stirring.The reaction mixture that obtains slowly stirred add in the water contain 5 hydrochloric acid (1000ml).The throw out that filtration obtains, washing (1000ml ethanol/water (80: 20)) is also filtered once more.It was made CBS011 down in dry 2 days at 50 ℃.
Preparation t-BOC polymkeric substance
CBS011 (29.95g) is dissolved in the mixture of dioxolane (135.8g) and DMF (40g).Time with 0.5hr adds di-t-butyl sodium bicarbonate (10.00g), salt of wormwood (6.50g) and 18-crown-6 (2.0g), and the mixture that obtains is at room temperature stirred 2hr.By being deposited in the water and separated product (37g, output 97.1%) (t-BOC CBS011) and 50 ℃ dry 2 days down.
1H NMR (DMSO-d
6In): δ 1.50 (9H, m).(1H s) does not have peak value at δ 8.10 places to compare CBS011 δ 8.10.
Embodiment 10
Repeat the step of embodiment 3 and 4, only coating solution comprises the composition of listing in the table 5.The dry weight of imageable layer is 1.5g/m
2
Table 5
| Composition | Parts by weight |
| t-BOC CBS011 | 17.25 |
| N13 | 30.82 |
| LB6564 | 41.65 |
| Viola crystallina | 1.99 |
| IR dyestuff A | 1.46 |
| IR dyestuff C | 0.47 |
| SILIKOPHENP50X | 5.96 |
| BYK 307 | 0.40 |
With the imageable element that obtains be stored in 55 ℃ following 3 days, as among the embodiment 3.Imageable element after the thermal treatment that obtains with CREO Trendsetter 3244 (Creo Inc., Burnaby, British Columbia, Canada) internally test pattern (icon 0) 100,200 and 300mJ/cm
2The imaging energy density under imaging, and develop and estimation removing value and optimum resolution, as shown in Example 3.
Other imageable element with 50% lineament with 200mJ/m
2Imaging is handled so that the processing speed of 750mm/min is as described above then.Be determined at the some size after immersing in the Astro/2-propanol/water, as embodiment 3.The result is as shown in table 6.
Table 6
| The minimum exposure that following result is required: | |||
| Removing value (mJ/cm 2) | Optimum resolution (mJ/cm 2) | ||
| 500mm/min | 1000mm/min | 500mm/min | 1000mm/min |
| 200 | 200 | 200 | 200 |
Table 6 (continuing)
| Immerse the some size after the following time in the Astro/2-propanol/water: | |||||
| 0 hour | 8 hours | 24 hours | |||
| 50％ | 100％ | 50％ | 100％ | 50％ | 100％ |
| 51 | 100 | 51 | 100 | 48 | 100 |
Embodiment 11
This embodiment has represented the preparation of the tosic acid ester derivative (tosyl group RAR-62) of RAR-62.RAR-62 (29.95g) is dissolved among dioxolane (135.8g) and the DMF (40g).In ice bath, be cooled to the mixture that obtains below 10 ℃ and remain on below 10 ℃, add Tosyl chloride (8.66g) with time of ten minutes simultaneously, add triethylamine (4.95g) with time of 15 minutes then.Mixture is stirred 15min being lower than under 15 ℃ the temperature.Time with 10sec adds acetic acid (2.77g), and with mixture restir 15min.
Add acidifying (acetic acid 2.77g) ice/water mixture (300g) in the mixture and stirred reaction mixture 5 minutes with several minutes times.Form the gelatinoid of viscosity.After each composition sedimentation, supernatant liquor inclines.Be dissolved in viscous substance in dioxolane/water (80: 20) and pour in the second acidifying ice/water mixture.The white precipitate (tolylsulfonyl RAR-62) that obtains is leached and drying.Output=34.95g (73.7%).IR：3379cm
-1(s)NH，1670cm
-1(s)N-CO-N，1367cm
-1(s)-SO
2-O-，1308cm
-1(s)-SO
2-，1197 & 1173cm
-1(s)-SO
2-O-，1093cm
-1(vs)-SO
2-，563cm
-1(s)-SO
2-。
1H NMR (DMSO-d
6In): δ 6.80 (4H, s).Do not observe peak value at δ 8.20 places.By contrast, RAR-62 have at δ 8.20 places peak value (1H, s).
Embodiment 12
This embodiment has represented tosic acid ester derivative (tosyl group EUV-5) synthetic of EUV-5.Repeat the step of embodiment 11, only use EUV-5 (29.95g) to replace RAR-62, and the usage quantity of other material is as follows: Tosyl chloride (6.71g), triethylamine (3.56g) and acetic acid (2.15g).Output=33.50g (70.7%).IR：3376cm
-1(s)NH，1672cm
-1(s)N-CO-N，1369cm
-1(s)-SO
2-O-，1309cm
-1(s)-SO
2-，1197 & 1173cm
-1(s)-SO
2-O-，1093cm
-1(vs)-SO
2-，564cm
-1(s)-SO
2-。
1H NMR (DMSO-d
6In): δ 6.80 (4H, s).Do not observe peak value at δ 8.20 places.By contrast, EUV-5 have at δ 8.20 places peak value (1H, s).
Embodiment 13 and 14 and comparative example 5 and 6
Bottom: by the material dissolves in the table 7 is made coating solution in 2-butanone/1-methoxyl group-Virahol/butyrolactone/water in (65/15/10/10).With the coiling rod each coating solution is coated on the base material A.The element that obtains is made of the bottom on the base material, and it is following dry 35 seconds at 135 ℃.The dry coating weight of lower floor is 1.3g/m
2
Table 7
| The embodiment sequence number | ||||
| C5 | 13 | C6 | 14 | |
| Composition | Parts by weight | |||
| RAR-62 | 15 | - | - | - |
| Tosyl group RAR-62 | - | 15 | - | - |
| EUV-5 | - | - | 15 | - |
| Tosyl group EUV-5 | - | - | - | 15 |
| Copolymer 1 | 59.65 | 59.65 | 59.65 | 59.65 |
| GP649D99 | 10 | 10 | 10 | 10 |
| IR dyestuff A | 15 | 15 | 15 | 15 |
| BYK 307 | 0.35 | 0.35 | 0.35 | 0.35 |
Imageable layer: the preparation of imageable layer such as embodiment 5, only functions of use novolac resin TN-13.The dry coating weight of imageable layer is 0.9g/m
2As embodiment 5, estimate the imageable element that obtains.The result as shown in Figure 8.
Table 8
| Embodiment | Goldstar TMDrop test (second) | The minimum exposure that following result is required: | Solvent tolerance drop test (second) | |||
| Bottom | Complete element | Removing value (mJ/cm 2) | Optimum resolution (mJ/cm 2) | DAA/ water | BC/ water | |
| C5 | 12 | 180 | 115 | 126 | 240 | 300 |
| 13 | 12 | 180 | 115 | 126 | 210 | 270 |
| C6 | 12 | 210 | 106 | 126 | 210 | 330 |
| 14 | 12 | 210 | 98 | 115 | 210 | 330 |
Table 8 (continuing)
The version that disappears test
| 210 ℃ of bakings down a | 230 ℃ of bakings down | |
| C5 | 3 | 2 |
| 13 | 4 | 2 |
| C6 | 3 | 2 |
| 14 | 3 | 2 |
a1=does not have imageable layer to be removed; The imageable layer of 5=50% is removed
Embodiment 15 and 16 and comparative example 7 and 8
This embodiment has represented the individual layer imageable element.As embodiment 3, utilize the material preparation imageable element of listing in the table 9.The dry weight of each imageable layer is 1.5g/m
2
Table 9
| The embodiment sequence number | ||||
| C7 | 15 | C8 | 16 | |
| Composition | Parts by weight | |||
| RAR-62 | 10 | - | - | - |
| Tosyl group RAR-62 | - | 10 | - | - |
| EUV-5 | - | - | 10 | - |
| Tosyl group EUV-5 | - | - | - | 10 |
| N-13 | 20 | 20 | 20 | 20 |
| LB6564 | 60.65 | 60.65 | 60.65 | 60.65 |
| Viola crystallina | 2 | 2 | 2 | 2 |
| IR dyestuff A | 2 | 2 | 2 | 2 |
| SILIKOPHEN P50X | 5 | 5 | 5 | 5 |
| BYK 307 | 0.35 | 0.35 | 0.35 | 0.35 |
As embodiment 3, estimate imageable element.The result is as shown in table 10.
Table 10
| The minimum exposure that following result is required: | ||||
| Removing value (mJ/cm 2) | Optimum resolution (mJ/cm 2) | |||
| 500mm/min | 1500 mm/min | 500mm/min | 1500 mm/min | |
| C7 | 150 | 150 | 150 | 150 |
| 15 | 150 | 150 | 150 | 150 |
| C8 | 150 | 150 | 150 | 150 |
| 16 | 150 | 150 | 150 | 150 |
Table 10 (continuing)
| Immerse Astro/2-following time of propanol/water point size afterwards | ||||
| 0 hour | 24 hours | |||
| 50％ | 100％ | 50％ | 100％ | |
| C7 | 50 | 100 | 52 | 100 |
| 15 | 52 | 100 | 52 | 100 |
| C8 | 50 | 100 | 52 | 100 |
| 16 | 54 | 100 | 52 | 100 |
Table 10 (continuing)
The version that disappears test
| 210 ℃ of bakings down a | 230 ℃ of bakings down | |
| C7 | 3 | 2 |
| 15 | 3 | 2 |
| C8 | 3 | 2 |
| 16 | 3 | 2 |
a1=does not have imageable layer to be removed; The imageable layer of 5=50% is removed
The present invention is illustrated, requires following claim and equivalent thereof now.
Claims (10)
1. multipolymer comprises the following material of polymerized form:
(a) about 1wt% is to the N-phenylmaleimide of about 30wt%, N-cyclohexyl maleimide, N-benzyl maleimide or its mixture;
(b) about 1wt% is to acrylamide, Methacrylamide or its mixture of about 30wt%;
(c) about 20% to about 75% vinyl cyanide, methacrylonitrile or its mixture; And
(d) the about 20wt% of total amount is selected from the monomeric monomer of following structure to one or more of about 75wt%:
CH
2＝C(R)-Z-X-NHC(O)NH-Y-R’
Wherein:
X is-[C (CH
3)
2]-or-[(CH
2)
n]-, wherein n is 0 to 12;
Y be adjacent-,-or right-[C
6H
4];
Z is-[C (O) O]-,-[C (O) NH]-or adjacent-,-or right-[C
6H
4]-;
R is hydrogen or C
1To C
4Alkyl;
R ' is-OC (O)-OR " ,-OC (O)-Ar or-OSO
2-Ar;
R " be C
1To C
12Alkyl, C
1To C
12Aralkyl, C
1To C
12Aryl, C
1To C
12Thiazolinyl or trimethyl silyl;
Ar is C
6H
5-n 'T
N ', wherein the total number of carbon atoms of Ar is six to ten;
Each T is independently selected from C
1To C
4Alkyl, fluoro, chloro, bromo, iodo, trifluoromethyl, methoxyl group and cyano group; And
N ' is 0 to 5 integer; And
Wherein this multipolymer dissolves in the pH value greater than about at least 11 basic solution.
2. the multipolymer of claim 1, wherein said multipolymer comprise the N-phenylmaleimide of about 3wt% of polymerized form to about 20wt%; Approximately 5wt% is to the Methacrylamide of about 2wt%; Approximately 35wt% is to the vinyl cyanide of about 60wt%; And total amount is about 30wt% to the monomer of one or more components (d) of about 60wt%, and wherein said multipolymer dissolves in the pH value greater than about at least 12 basic solution.
3. claim 1 or 2 multipolymer, wherein R is hydrogen or methyl; X is-[C (CH
3)
2]-or-[(CH
2)
2]-; Y is right-[C
6H
4]-.
4. each multipolymer of claim 1 to 3, wherein Z be-[C (O) O]-or-[C
6H
4]-.
5. each multipolymer of claim 1 to 4, wherein R ' is-OC (O)-OR ".
6. each multipolymer of claim 1 to 4, wherein R ' be-OC (O)-Ar or-OSO
2-Ar.
7. imageable element, it comprises the imageable layer on the carrier, wherein said imageable element comprises in optical-thermal conversion material and the claim 1 to 6 each multipolymer.
8. the imageable element of claim 7, wherein said imageable element is the individual layer imageable element, and described imageable layer comprises multipolymer, optical-thermal conversion material and (1) novolac resin and dissolution inhibitor, and (2) comprise the novolac resin of polar group, or (3) its mixture.
9. the imageable element of claim 7, wherein said element is a sandwich type element, it comprises imageable layer, bottom and base material in proper order;
Wherein:
Described imageable layer comprises (1) novolac resin and dissolution inhibitor, and (2) comprise the phenolic varnish of polar group, or (3) its mixture; And
Described bottom comprises described multipolymer, described optical-thermal conversion material and tackiness agent.
10. method that forms image, described method comprises step:
In the thermal imaging claim 7 to 9 arbitrary imageable element and be formed into picture after imageable element, comprise imaging and imaging region not in its imageable layer;
With photographic developer develop described imaging imageable element and remove described imaging region, comprise the printing plate of described image with formation; And
Toast described printing plate.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US82054604A | 2004-04-08 | 2004-04-08 | |
| US10/820,546 | 2004-04-08 | ||
| US11/072,486 | 2005-03-04 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1946753A true CN1946753A (en) | 2007-04-11 |
Family
ID=38045483
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200580012150 Pending CN1946753A (en) | 2004-04-08 | 2005-03-25 | Positive-working, thermally sensitive imageable element |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1946753A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103881025A (en) * | 2012-12-21 | 2014-06-25 | 乐凯华光印刷科技有限公司 | Anti-solvent vinyl polymer with multilayer structure, synthetic method thereof and applications thereof |
| 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 |
-
2005
- 2005-03-25 CN CN 200580012150 patent/CN1946753A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103881025A (en) * | 2012-12-21 | 2014-06-25 | 乐凯华光印刷科技有限公司 | Anti-solvent vinyl polymer with multilayer structure, synthetic method thereof and applications thereof |
| CN103881025B (en) * | 2012-12-21 | 2016-03-30 | 乐凯华光印刷科技有限公司 | The solvent resistant type vinyl polymer of multi-ply construction and preparation method and use thereof |
| 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 |
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