CN101821097B - A lithographic printing plate precursor - Google Patents

A lithographic printing plate precursor Download PDF

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Publication number
CN101821097B
CN101821097B CN200880110738.6A CN200880110738A CN101821097B CN 101821097 B CN101821097 B CN 101821097B CN 200880110738 A CN200880110738 A CN 200880110738A CN 101821097 B CN101821097 B CN 101821097B
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plate precursor
surfactant
coating
fluoroalkyl
integer
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CN101821097A (en
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H·范阿尔特
A·梅斯特斯
S·林吉尔
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Agfa NV
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Agfa Gevaert AG
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C1/00—Forme preparation
    • B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
    • B41C1/1008—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C1/00—Forme preparation
    • B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
    • B41C1/1008—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials
    • B41C1/1016—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials characterised by structural details, e.g. protective layers, backcoat layers or several imaging layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2201/00—Location, type or constituents of the non-imaging layers in lithographic printing formes
    • B41C2201/02—Cover layers; Protective layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2201/00—Location, type or constituents of the non-imaging layers in lithographic printing formes
    • B41C2201/04—Intermediate layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2201/00—Location, type or constituents of the non-imaging layers in lithographic printing formes
    • B41C2201/14—Location, type or constituents of the non-imaging layers in lithographic printing formes characterised by macromolecular organic compounds, e.g. binder, adhesives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/02—Positive working, i.e. the exposed (imaged) areas are removed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/06—Developable by an alkaline solution
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/22—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by organic non-macromolecular additives, e.g. dyes, UV-absorbers, plasticisers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/24—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by a macromolecular compound or binder obtained by reactions involving carbon-to-carbon unsaturated bonds, e.g. acrylics, vinyl polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/26—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by a macromolecular compound or binder obtained by reactions not involving carbon-to-carbon unsaturated bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/26—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by a macromolecular compound or binder obtained by reactions not involving carbon-to-carbon unsaturated bonds
    • B41C2210/262—Phenolic condensation polymers, e.g. novolacs, resols

Abstract

A heat-sensitive positive-working lithographic printing plate precursor is disclosed which comprises on a support having a hydrophilic surface or which is provided with a hydrophilic layer, a heat and/or light-sensitive coating comprising a surfactant, characterized in that said surfactant comprises a polyether block including a pendant fluoroalkylgroup and a urethane linking group.

Description

Lighographic printing plate precursor
The field of the invention
The present invention relates to Lighographic printing plate precursor (lithographic printing plateprecursor).
Background of the present invention
Offset press uses so-called printing original edition plate (printing master) like galley, and it is installed on the cylinder of printing machine.Master carries lithographic image in its surface and upward obtains printed matter through being applied to printing ink on the image and then printing ink being transferred to reception material (it typically is a paper) from master.In common, so-called " wetting " lithographic printing; Printing ink and water-based fountain solution (fountain solution) (also be known as and soak liquid) are supplied to by lipophile (or hydrophobicity; Be that printing ink is accepted, water repels) on the lithographic image formed of zone and hydrophily (or oleophobic property, promptly water is given and accepted, printing ink repels) zone.In so-called driography, this lithographic image is given and accepted by printing ink and printing ink antitack agent (printing ink repulsion) zone is formed and in the driography process, only printing ink is supplied to this master.
Printing original edition plate normally obtains through the processing that exposes (expose) and image forming material (being called plate precursor) with image mode to the open air.Except that well-known photosensitive, the version of so-called pre-sensitized (it is adapted to pass through the UV contact exposure that film mask (film mask) is carried out) also has the plate precursor of temperature-sensitive welcome in nineteen nineties.This type of fuel factor material provides the advantage of sunlight stability and has been particularly useful for so-called " computer-arrive-version " method, and wherein this plate precursor directly exposes to the open air, does not promptly use film mask.This material is exposed to heat or is exposed to infrared light and can trigger (physics) chemical process with the heat that produced, and as ablating, polymerisation is utilized the crosslinked not dissolving that realizes of polymer, the particle aggregation of thermoinducible solubilization or thermoplastic polymer latex.
Most popular temperature-sensitive forme through coating expose to the open air and non-exposed areas between thermoinducible dissolubility difference in alkaline developer form image.Coating typically comprises the lipophile binding agent, phenolic resins for example, and wherein its dissolution velocity in developer descends (negativity) or increases (positivity) through exposing to the open air with image mode.In process, difference in solubility causes non-image (non-printing) regional removing of coating, therefore expose hydrophilic carrier, and the image of coating (printing) zone is retained on the carrier still.The exemplary of this type of edition for example is described among the EP-A 625728,823327,825927,864420,894622 and 901902.According to for example EP-625, described in 728, the negativity embodiment of this type of fuel factor material usually need expose to the open air and develop between preheating step.
At EP-As 770494,770495, described in 770496 and 770497, do not need the negativity plate precursor of preheating step can contain image recording layer according to for example through the thermal induction particle aggregation effect of thermoplastic polymer particles (latex).These patents disclose the method for making lithographic plate; It may further comprise the steps: (1) will comprise and be dispersed in hydrophilic agglomerant and can light be changed into that the image-forming component of hydrophobic thermoplastic polymer's particle in the compound of heat exposes to the open air with image mode and develop the element that image mode exposes to the open air through applying fountain solution and/or printing ink (2).
In these heat processing techniques some allow not have plate-making under the situation of wet process and for example to be that ablation with one or more coatings is the basis.In exposed areas, exposed the surface of bottom, this surface has the different affinitys to printing ink or fountain solution with not exposing to the open air between the coating surface.
At other hot-working method that does not have under the situation of wet process the plate-making of allowing for example is the method that is converted into the basis with the thermal induction hydrophily/lipophile of one or more coatings, on exposed areas, has produced like this and is not exposing the surperficial different affinity to printing ink or fountain solution of coating to the open air.
JP 2006/330670 discloses the plate precursor that contains coating, and this coating comprises the spreader-sticker that comprises fluoroalkyl.
Plate precursor subjects in transportation, mechanical handling and/or manual handling process by the caused damage of mechanical force that puts on the coating surface.After coating and drying, the temperature-sensitive plate precursor is cut, piles up and be packaged in the box by means of the packaging facilities of regulation.In the transmission course of the plate precursor of packing, these versions move relative to each other.This degree of slip can be measured through piling up the static friction coefficient of measuring between the precursor at two: between the surface of plate precursor and the intermediate in the above or for the low static friction coefficient of the situation of not using intermediate between the aluminium back side of the surface of plate precursor and version in the above, cause the version of slippage.The version of slippage not only causes dangerous situation in transportation, and causes the lip-deep damage at plate precursor, the formation of for example well-known " scratch ".Consider that from aesthetic property scratch is unacceptable, still, in addition, these scratch zones of coating in printing process usually fully absorbing ink and cause difference, unacceptable printing quality sometimes.On the other hand, be the slipping property that the plate precursor of characteristic will have much less with surface, but in general, the preparation of this type of plate precursor under industry coating and drying condition (being coating performance) is difficult with high static friction coefficient.As a result, obtained to have plate precursor irregular and uneven surface (being also referred to as surface in the prior art) with bad appearance of coat.Therefore, the very difficult appearance of coat that obtains to have with excellence is the plate precursor on the surface of characteristic with high static friction coefficient of while under industry coating and drying condition.
General introduction of the present invention
The purpose of this invention is to provide the plate precursor with temperature-sensitive and/or photosensitive coating, this coating has smooth, smooth and is surperficial uniformly, and it has sufficiently high coefficient of friction simultaneously; Promptly make the plate precursor that in loading and unloading and/or transmission course, piles up be not easy the coefficient of friction that moves each other.
This purpose is that the positivity Lighographic printing plate precursor of temperature-sensitive is realized through claim 1, and this precursor is included in the possess hydrophilic property surface or provides temperature-sensitive that comprises surfactant and/or the photosensitive coating on the carrier of hydrophilic layer,
It is characterized in that this surfactant comprises polyether block, this block comprises fluothane side group and urethane linking group.
Find amazingly; Opposite with the surfactant of prior art, the surfactant that is used for the present invention is not merely coating and the good appearance of coat of good coating performance-be is provided or has the coating of smooth and smooth surface-but the coating with sufficiently high coefficient of friction is provided simultaneously.
Further feature of the present invention, key element, step, characteristic and advantage will become clearer from the preferred embodiment of following detailed description of the present invention.
Detailed description of the present invention
Lighographic printing plate precursor of the present invention is included in temperature-sensitive and/or the photosensitive coating on the carrier.The imaging mechanism of this type of plate precursor can be through directly being exposed to heat (for example by means of thermal print head (thermal head)) or through in coating, can the light absorption of one or more compounds that light (more preferably infrared light) changes into heat being triggered.
This coating comprises the surfactant that comprises polyether block, and this polyether block comprises fluothane side group and urethane linking group.This fluoroalkyl can be straight or branched and comprise-(CF 2)-with-(CHF)-unit.The quantity of this type of unit can be 1, promptly-and (CF 3) ,-(CHF 2) or-(CH 2F); Or, preferably be lower than 20 greater than 1; More preferably less than 15 with most preferably between 2 and 10.
In preferred embodiments, this polyether block comprises alkoxyl fluoroalkyl side group.This alkoxyl fluoroalkyl comprises-[(CR aR b) g-O-(CR cR d) h-fluoroalkyl]-unit, wherein R a, R b, R cAnd R dRepresenting hydrogen independently, alkyl or fluoroalkyl and g and h represent independently>=0 integer.
The urethane linking group that is present in the surfactant can be connected in the polyether block that comprises fluothane side group and/or alkoxyl fluoroalkyl side group; Maybe can be connected in optional being present on the another kind of polymer blocks such as polyethers, polyester, polyurethane or polyvinyl alcohol block in this surfactant.
Be used for surfactant of the present invention and preferably include construction unit by following formula (I) expression:
Figure GPA00001088352000041
(I)
Wherein
A and b represent independently >=0 integer;
C is illustrated in the integer between 1 and 40, preferably the integer between 2 and 20;
Y 1Expression fluoroalkyl or alkoxyl fluoroalkyl;
Y 2Expression hydrogen; Optional substituted alkyl such as methyl, ethyl, propyl group, isopropyl, butyl, the tert-butyl group or amyl group, fluoroalkyl or alkoxyl fluoroalkyl;
R 1-R 4Represent hydrogen independently, fluoride, optional substituted alkyl is methyl, ethyl, propyl group, isopropyl, butyl, the tert-butyl group or amyl group for example; Fluoroalkyl or optional substituted aryl.
Optional substituting group on alkyl or aryl can be halogen such as F, Cl, Br or I; Alkyl or fluoroalkyl.
This fluoroalkyl and alkoxyl fluoroalkyl are like above definition.
In a more preferred embodiment, this surfactant comprises the construction unit by general formula (I) expression, wherein:
A and b represent independently >=0 integer;
C is illustrated in the integer between 1 and 40, preferably the integer between 2 and 20;
Y 1Expression fluoroalkyl or alkoxyl fluoroalkyl;
Y 2Expression hydrogen; Optional substituted alkyl such as methyl, ethyl, propyl group, isopropyl, butyl, the tert-butyl group or amyl group;
R 1-R 4Represent hydrogen independently, fluoride, optional substituted alkyl is methyl, ethyl, propyl group, isopropyl, butyl, the tert-butyl group or amyl group for example; Fluoroalkyl or optional substituted aryl.Optional substituting group on alkyl or aryl can be halogen such as F, Cl, Br or I; Alkyl or fluoroalkyl.
This fluoroalkyl and alkoxyl fluoroalkyl are like above definition.
In most preferred embodiment, this surfactant comprises polyether block, and this polyether block comprises alkoxyl fluoroalkyl side group and the urethane linking group of being represented by formula (II):
Figure GPA00001088352000051
(II)
Wherein d and e represent >=0 integer;
X representes fluoroalkyl;
Y 3Expression hydrogen or optional substituted alkyl such as methyl, ethyl, propyl group, isopropyl, butyl, the tert-butyl group or amyl group;
And f is illustrated in the integer between 1 and 40, preferably the integer between 2 and 20.
Optional substituting group on alkyl can be halogen such as F, Cl, Br or I; Alkyl or fluoroalkyl.
The surfactant that is used for the present invention may further include the one or more polyether blocks by general formula (III) expression:
Figure GPA00001088352000052
(III)
R wherein 5Expression hydrogen; Optional substituted alkyl or cycloalkyl such as methyl, ethyl, propyl group, isopropyl, cyclopenta; Optional substituted aryl, aralkyl or assorted alkyl;
And k is illustrated in the integer between 1 and 40, preferably the integer between 2 and 20.Optional substituting group on alkyl or aryl can be halogen such as F, Cl, Br or I; Alkyl or fluoroalkyl.
By general formula (I) and/or (II) construction unit of expression can link together and/or they can be chosen wantonly via linking group and are connected to the polyether block by formula (III) expression, on polyester, polyurethane or the polyvinyl alcohol block, constitute diblock copolymer.Through further connection diblock copolymer, can form segmented copolymer.
This type of diblock copolymer can be for example through the monohydroxy terminal that will comprise fluothane side group or alkoxyl fluoroalkyl side group polyethers with single-, two-or one of polyisocyanate compound, two or more isocyanate functional group react, the optional residual isocyanate functional group that carries out subsequently prepares with the reaction of optional polyethers, polyester, polyurethane or the polyvinyl alcohol that comprises fluothane side group or alkoxyl fluoroalkyl side group.Contain two or more hydroxyl end groups if comprise the hydroxy terminal polyethers of fluothane side group or alkoxyl fluoroalkyl side group, then can through with single-, two-and/or the polyisocyanate compound reaction obtain three blocks or segmented copolymer.These three-or segmented copolymer can comprise for example structure unit:
Figure GPA00001088352000061
Figure GPA00001088352000062
Wherein independently in each of above structural formula, m, n, o, p and w represent the integer between 1 and 40 independently, the integer between preferred 2 and 20.
Comprising the polyethers of the hydroxy terminal of fluothane side group or alkoxyl fluoroalkyl side group can be for example obtain through fluoroalkyl or the substituted oxetanes of alkoxyl fluoroalkyl and as the cationic ring-opening polymerization between the alcohol of initator.The alcohol initator can be alcohol or polyfunctional alcohol such as glycol, triol or the tetrol of simple function.They can have low-molecular-weight (being non-polymer) maybe can be polymeric alcohol such as condensation polymer for example single-or polyurethane, polyester or the polyethers at dihydroxy terminal or addition polymer polyvinyl alcohol for example.When this alcohol is simple function, obtain the fluoroalkyl and/or the alkoxyl fluoroalkyl polyethers at monohydroxy terminal; When this alcohol when being polyfunctional, obtain the fluoroalkyl and/or the alkoxyl fluoroalkyl polyethers at polyhydroxy terminal, for example two-, three-or (star-branched) fluoroalkyl and/or the alkoxyl fluoroalkyl polyethers of four-hydroxy terminal.
The suitable fluoroalkyl and the alkoxyl fluoroalkyl replacement oxetanes that are used for the preparation of surfactant comprise:
HFPO:
Figure GPA00001088352000072
Perfluor epoxy iso-butane (perfluoroisobutene oxide):
Figure GPA00001088352000073
Trifluoro (1,1,2,2-tetrafluoro ethyl)-oxirane:
Figure GPA00001088352000081
6-hydrogen perfluor-1,2-epoxy radicals hexane:
Figure GPA00001088352000082
Trifluoro (nine fluorine butyl) oxirane:
Figure GPA00001088352000083
2,2-two fluoro-3-phenyl-3-(trifluoromethyl)-oxirane:
Figure GPA00001088352000084
(seven fluoropropyls)-) oxirane,
Figure GPA00001088352000085
(seven fluoropropyls)-) oxirane:
2, two (trifluoromethyl) oxirane of 2-:
Figure GPA00001088352000091
Trifluoromethyl oxirane:
Figure GPA00001088352000092
[[2,3,3,3-tetrafluoro-2-(seven fluorine propoxyl group) propoxyl group] methyl]-oxirane:
Figure GPA00001088352000093
[[2,3,3,3-tetrafluoro-2-[1,1,2,3,3,3-hexafluoro-2-(seven fluorine propoxyl group) propoxyl group] propoxyl group] methyl]-oxirane:
Figure GPA00001088352000094
3-(2,2,2-trifluoro ethoxy methyl)-3-methyl oxetanes:
3-methyl-3-[(2,2,3,3,3-five fluorine propoxyl group) methyl] oxetanes:
Figure GPA00001088352000101
3-methyl-3-[[(2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-15 fluorine octyl groups) oxygen base] methyl]-oxetanes:
Figure GPA00001088352000102
3, two [(2,2, the 2-trifluoro ethoxy) the methyl]-oxetanes of 3-:
Figure GPA00001088352000103
3,3,4,4,5,5,6,6,7,7,8,8,8-ten trifluoro octyl group oxygen ylmethyl-3-methyl oxetanes:
Figure GPA00001088352000104
3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-17 fluorine decyl oxygen ylmethyl-3-methyl oxetanes:
3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-21 fluorine decyl oxygen ylmethyl-3-methyl oxetanes:
Figure GPA00001088352000111
3, two (2,2,3,3,4,4,4-seven fluorine the butoxymethyl)-3-oxetanes of 3-:
Figure GPA00001088352000112
3-methyl-3-[[(3,3,4,4,5,5,6,6,7,7,8,8,8-ten trifluoro octyl groups) oxygen base] methyl] oxetanes:
Figure GPA00001088352000113
3, two [[(2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-15 fluorine octyl groups) oxygen base] the methyl]-oxetanes of 3-:
Figure GPA00001088352000114
3-(2,2,3,3,4,4,4-seven fluorine butoxymethyl)-3-methyl oxetanes:
3-[(2,2,3,3,4,4,4-seven fluorine butoxy) methyl]-3-methyl oxetanes:
Figure GPA00001088352000121
3-[(2,2,3,3,4,4,4-seven fluorine butoxy) methyl]-3-methyl oxetanes:
Figure GPA00001088352000122
2,2,3,4-tetrafluoro-4-[1,2,2,2-tetrafluoro-1-[1,1,2,3,3,3-hexafluoro-2-(seven fluorine propoxyl group) propoxyl group] ethyl]-3-(trifluoromethyl)-oxetanes:
Figure GPA00001088352000123
2,2,3,4-tetrafluoro-4-[1,1,3,4,4,6,7,7,9,10,10,12,12,12-ten tetrafluoros-3,6,9-three (trifluoromethyl)-2,5,8,11-four oxa-s dodecane-1-yl]-3-(trifluoromethyl)-oxetanes:
Figure GPA00001088352000124
2,3,3-three fluoro-2-[1,1,2,3,3,3-hexafluoro-2-(seven fluorine propoxyl group) propoxyl group]-oxetanes:
Figure GPA00001088352000125
The suitable isocyanates that is used for the surfactant preparation comprises the isocyanates such as the phenyl isocyanate of simple function, stearyl isocyanates, 2-(methacryloxy) ethyl isocyanate; Methyl isocyanate, isocyanato-cyclohexane, ethyl isocyanate; 1-(isocyanato-methyl) benzene; 4-methoxybenzene based isocyanate, isopropyl isocyanate, m-anisyl isocyanates and 2-tolyl isocyanates; Vulcabond is as 1,6-hexylidene diisocyanate, 4,4 '-methyl diphenylene diisocyanate; Isoflurane chalcone diisocyanate, toluene di-isocyanate(TDI) (tolylene diisocyanate), 4,4 '-two isocyanos-dicyclohexyl methyl hydride; 1,4-phenylene vulcabond, tetramethylene isocyanates; Ten dimethylene diisocyanates, 1,5-naphthalene diisocyanate and m-eylylene diisocyanate; Or the isocyanurate trimer of polyfunctional isocyanate such as hexamethylene diisocyanate.
Described specific vulcabond is following IPDI:
Figure GPA00001088352000131
Can connect by formula (I), (II) and/or (III) construction unit and/or other polymer blocks linking group of polyester, polyurethane or polyvinyl alcohol block for example of expression; Can having at the most, 20 carbon atoms are selected from C with containing; H, N, at least one atom among O and the S.Preferred linking group is the linear alkylene with 1-18 carbon atom, has linearity, branching or the cyclic group of 3-18 carbon atom, has the alkynylene and the arlydene with 6-20 atom ,-O-of 2-18 carbon atom;-S-,-CO-,-CO-O-;-O-CO-,-CS-,-NR nR o-,-CO-NR n-,-NR n-CO-,-NR n-CO-O-,-O-CO-NR n-,-NR n-CO-NR o-,-NR n-CS-NR o-, phenylene, naphthyl, anthryl, heterocyclic radical, or their combination, wherein R nAnd R oRepresent hydrogen or optional substituted alkyl, alkenyl, alkynyl, cycloalkyl, heterocycle, aryl, heteroaryl, aralkyl or heteroarylalkyl independently of one another.Preferred substituted on these groups is to have alkoxyl, halogen or the hydroxyl of 12 carbon atoms at the most in the back.
The suitable example of diblock and many blocks surfactant comprises surfactant down:
Figure GPA00001088352000141
Figure GPA00001088352000142
Figure GPA00001088352000143
Figure GPA00001088352000144
Figure GPA00001088352000151
Figure GPA00001088352000152
Figure GPA00001088352000153
Figure GPA00001088352000154
Figure GPA00001088352000155
Figure GPA00001088352000161
Figure GPA00001088352000162
Figure GPA00001088352000163
Figure GPA00001088352000164
Figure GPA00001088352000165
Wherein independently in each in above structure, m, n, o, p, r, s, t, x, y, u, q and v are illustrated in the integer between 1 and 40 independently, preferably the integer between 2 and 20.
The amount of surfactant is preferably between 0.05%wt and 5%wt, more preferably between 0.1%wt and the 3%wt and most preferably between 0.15%wt and 1.5%wt in coating.
Temperature-sensitive plate precursor (thermal printing plate precursor) comprises temperature-sensitive and/or photosensitive coating and is positivity.Its operation principle is that the thermal induction solubilization with oleophilic resin is the basis.This oleophilic resin preferably dissolves in the water-based developer, more preferably dissolves in the polymer in the water-based alkaline-based developer of pH between 7.5 and 14.Preferred polymer is a for example novolac of phenolic resins, resol (resole), polyvinyl phenol and carboxyl substituted polymer.The exemplary of these polymer is described in DE 4007428, among DE 4027301 and the DE 4445820.With respect to the gross weight of the whole components that in coating, exist, the amount of the phenolic resins that in coating, exists is 50wt% at least preferably, preferably 80wt% at least.This oleophilic resin is phenolic resins preferably, and wherein this phenyl or this hydroxyl carry out chemical modification with organic substituent.Phenolic resins with the organic substituent chemical modification can demonstrate the chemical-resistant to the raising of printing chemicals such as fountain solution or galley treat liquid such as galley cleaning agent.The example of this type of chemical modification phenolic resins is described in EP 934 822; EP 1 072 432; US 5,641, and 608; EP 982123; WO 99/01795; EP 2 102 446, and EP 2 102 444; EP 2 102 445; EP 2 102 443; EP 3 102 522; WO04/035310; WO04/035686; WO04/035645; Among WO04/035687 or the EP 1,506 858.The modified resins that is described among the EP 2 102 446 is preferred; Especially wherein the phenyl of this phenolic resins is had substituted those resins of group of structure-N=N-Q, wherein-the N=N-group be bonded on the carbon atom of phenyl with covalent bond and wherein Q be aromatic group.
Novolac resin or resol can prepare through at least a material that in the presence of acid catalyst, is selected from aromatic hydrocarbon and the polycondensation reaction that is selected from least a aldehydes or ketones of aldehydes and ketone, and this aromatic hydrocarbon is (benzene) phenol for example, neighbour-cresols, paracresol, metacresol; 2,5-xylenols, 3,5-xylenols, resorcinol; Burnt training phenol, bis-phenol, bisphenol-A, trisphenol, neighbour-ethyl-phenol; Right-ethyl-phenol, propylphenol, normal-butyl phenol, tert-butyl phenol, 1-naphthols and beta naphthal; This aldehydes such as formaldehyde, glyoxal, acetaldehyde, propionic aldehyde, benzaldehyde and furfural, and this ketone such as acetone, methyl ethyl ketone and methyl iso-butyl ketone (MIBK).Replace formaldehyde and acetaldehyde, can use paraformaldehyde (paraformaldehyde) and paraaldehyde (paraldehyde) respectively.
The weight average molecular weight of novolac resin (by using the common correction and the gel permeation chromatography measurement of polystyrene standards) is 500-150 preferably, 000g/mol, more preferably 1,500 to 50,000g/mol.
Gather the monomer that (vinyl phenol) resin also can be one or more hydroxyl phenyl such as the polymer of hydroxy styrenes or (methyl) crylic acid hydroxylphenyl base ester.The example of this type of hydroxy styrenes is neighbour-hydroxy styrenes ,-hydroxy styrenes, right-hydroxy styrenes, 2-(neighbour-hydroxy phenyl) propylene, 2-(-hydroxy phenyl) propylene and 2-(right-hydroxy phenyl) propylene.This type of hydroxy styrenes can be had has substituting group such as chlorine, bromine, iodine, fluorine or C on its aromatic ring 1-4Alkyl.The example of this type of (methyl) crylic acid hydroxylphenyl base ester is methacrylic acid 2-hydroxyl-phenylester.
Gathering (vinyl phenol) resin can prepare through the monomer of one or more hydroxyl phenyl of polymerization in the presence of radical initiator or cationic polymerization initiators usually.This gathers (vinylphenol) resin also can be through one or more monomer and other monomeric compound such as the acrylate monomer of these hydroxyl phenyl of combined polymerization; Methacrylate monomer; Acrylamide monomer; Methyl acrylamide monomer, vinyl monomer, aromatic vinyl monomer or diene monomers prepare.
This weight average molecular weight (through using common correction and polystyrene standards) of gathering (vinyl phenol) resin preferably 1,000 to 200 by gel permeation chromatography measurement, 000g/mol, more preferably 1,500 to 50,000g/mol.
The example of phenolic resins is:
-ALNOVOL TMSPN452 is at Dowanol TMThe novolac resin of 40%wt among the PM can be purchased from CLARIANT GmbH.
-ALNOVOL TMSPN400 is at Dowanol TMThe novolac resin of 44%wt among the PMA can be purchased from CLARIANT GmbH.
-ALNOVOL TMHPN100, the novolac resin that can be purchased from CLARIANT GmbH.
-DURITE TMPD443, the novolac resin that can be purchased from BORDEN CHEM.INC.
-DURITE TMSD423A, the novolac resin that can be purchased from BORDEN CHEM.INC.
-DURITE TMSD126A, the novolac resin that can be purchased from BORDEN CHEM.INC.
-BAKELITE TM6866LB02, the novolac resin that can be purchased from BAKELITE AG.
-BAKELITE TM6866LB03, the novolac resin that can be purchased from BAKELITE AG.
-KR 400/8, the novolac resin that can be purchased from KOYO CHEMICALS INC.
-HRJ 1085, the novolac resin that can be purchased from SCHNECTADY INTERNATIONAL INC.
-HRJ 2606, the novolac resin that can be purchased from SCHNECTADY INTERNATIONAL INC.
-LYNCUR TMCMM, the 4-hydroxyl-styrene that can be purchased from SIBER HEGNER and the copolymer of methyl methacrylate.
This coating can comprise the second layer, and the latter comprises: the polymer or the copolymer (promptly (being total to) polymer) that comprise at least a monomeric unit that contains at least one sulfuryl amine group.This layer is between the above layer that comprises lipophilic resin and hydrophilic carrier.Below, ' (being total to) polymer that comprises at least a monomeric unit that contains at least one sulfuryl amine group ' also is called as " sulfonamide (being total to) polymer ".This sulfonamide (being total to) polymer is preferably alkali-soluble.This sulfuryl amine group is preferably by-NR-SO 2-,-SO 2-NR-or-SO 2-NRR ' expression, wherein R and R ' represent hydrogen or organic substituent independently of one another.
The surfactant that is used for the present invention may reside in ground floor, the second layer or optional other layer.Most preferably, surfactant is present in the layer that comprises lipophilic resin.
Sulfonamide (being total to) polymer is the homopolymerization of the monomeric unit through containing at least one sulfuryl amine group or the prepared high-molecular weight compounds of copolymerization through this type of monomeric unit and other polymerisable monomeric unit preferably.
The example that contains the monomeric unit of at least one sulfuryl amine group comprises the monomeric unit that further contains at least one polymerisable unsaturated bond such as acryloyl group, pi-allyl or vinyl oxygen base.Suitable example has been disclosed in U.S.5, and 141,838, EP 1 545 878; EP909,657, among EP O 894 622 and the EP 1,120,246.
Comprise with the example of the monomeric unit of the monomeric unit combined polymerization that contains at least one sulfuryl amine group being disclosed in EP 1,262,318, EP 1,275,498, and EP 909,657, EP1,120,246, the monomeric unit among EP O 894 622 and the EP 1,400,351.
Sulfonamide (being total to) polymer and/or their preparation method's suitable example has been disclosed in EP-A 933 682, and EP-A 982 123, and EP-A 1 072 432, and WO 99/63407 and EP1 are in 400,351.
The highly preferred example of sulfonamide (being total to) polymer is homopolymers or the copolymer that comprises by the construction unit of following general formula (IV) expression:
Figure GPA00001088352000201
(IV)
Wherein:
R 9Represent hydrogen or have the alkyl of 12 carbon atoms at the most; Preferred R 9Expression hydrogen or methyl;
X 1Expression singly-bound or divalent linker.This divalent linker has at the most, and 20 carbon atoms are selected from C, H, N, at least one atom among O and the S with containing.Preferred divalent linker is the linear alkylene with 1-18 carbon atom, has linearity, branching or the cyclic group of 3-18 carbon atom, has the alkynylene and the arlydene with 6-20 (carbon) atom ,-O-of 2-18 carbon atom;-S-,-CO-,-CO-O-;-O-CO-,-CS-,-NR nR o-,-CO-NR n-,-NR n-CO-,-NR n-CO-O-,-O-CO-NR n-,-NR n-CO-NR o-,-NR n-CS-NR o-, phenylene, naphthyl, anthryl, heterocyclic radical, or their combination, wherein R nAnd R oRepresent hydrogen or optional substituted alkyl, alkenyl, alkynyl, cycloalkyl, heterocycle, aryl, heteroaryl, aralkyl or heteroarylalkyl independently of one another.Preferred substituted on these groups is to have alkoxyl, halogen or the hydroxyl of 12 carbon atoms at the most in the back.Preferred X 1Be methylene, ethylidene, propylidene, butylidene, isopropylidene, cyclohexylidene, phenylene, toluylene (tolylene) or biphenylene;
Y 4Be by-NR p-SO 2-or-SO 2-NR qThe divalence sulfuryl amine group of-expression, wherein R pAnd R qRepresent hydrogen independently of one another, optional substituted alkyl, alkanoyl (alkanoyl), alkenyl, alkynyl, cycloalkyl, heterocycle, aryl, heteroaryl, aralkyl or heteroarylalkyl or structural formula-C (=N)-NH-R 10Group, R wherein 10Expression hydrogen or optional substituted alkyl or aryl;
Z 1Expression end group, the preferably alkylidene of hydrogen or optional substituted linearity, branching or ring-type or have the alkyl such as the methyl of 1 to 18 carbon atom, ethyl, propyl group; Isopropyl, butyl, isobutyl group, the tert-butyl group; Sec-butyl, amyl group, hexyl, cyclopenta; Cyclohexyl, octyl group, optional substituted arlydene or have the aryl of 6 to 20 carbon atoms; Optional substituted heteroarylidene or heteroaryl; Alkylene group or alkenyl with linearity, branching or ring-type of 2 to 18 carbon atoms, alkynylene or alkynyl with linearity, branching or ring-type of 2 to 18 carbon atoms, or alkoxyl.
Choose wantonly at Z 1The example of the preferred substituents that exists on these groups of expression is to have the alkyl of 12 carbon atoms at the most, has the alkoxyl of 12 carbon atoms, halogen atom or hydroxyl at the most.
Construction unit by formula (IV) expression preferably has following groups:
X 1The expression alkylidene, cyclohexylidene, phenylene or toluylene ,-O-,-S-,-CO-,-CO-O-,-O-CO-,-CS-,-NR nR o-,-CO-NR n-,-NR n-CO-,-NR n-CO-O-,-O-CO-NR n-,-NR n-CO-NR o-,-NR n-CS-NR o-, or their combination and R wherein nAnd R oRepresent hydrogen or optional substituted alkyl, alkenyl, alkynyl, cycloalkyl, heterocycle, aryl, heteroaryl, aralkyl or heteroarylalkyl independently of one another.Preferred substituted on these groups is to have the alkoxyl of 12 carbon atoms at the most, halogen or hydroxyl in the back;
Y 4Be by-NR p-SO 2-,-SO 2-NR qThe divalence sulfuryl amine group of-expression, wherein R pAnd R qRepresent hydrogen independently of one another, optional substituted alkyl, alkanoyl, alkenyl, alkynyl, cycloalkyl, heterocycle, aryl, heteroaryl, aralkyl or heteroarylalkyl;
Z 1Be end group, and be expression hydrogen, alkyl such as methyl, ethyl, propyl group, isopropyl, butyl; Isobutyl group, the tert-butyl group, sec-butyl, amyl group, hexyl, cyclopenta, cyclohexyl or octyl group; Benzyl, optional substituted aryl or heteroaryl, naphthyl, anthryl, pyridine radicals, pi-allyl or vinyl.
The specific preferred example of sulfonamide (being total to) polymer is to comprise N-(right-the amino-sulfonyl phenyl) (methyl) acrylamide, the polymer of N-(-amino-sulfonyl phenyl) (methyl) acrylamide and/or N-(neighbour-amino-sulfonyl phenyl) (methyl) acrylamide.Preferred especially sulfonamide (being total to) polymer is the polymer that comprises N-(right-the amino-sulfonyl phenyl) Methacrylamide; Wherein sulfuryl amine group comprises optional substituted straight chain, branching, ring-type or Heterocyclylalkyl, optional substituted aryl or optional substituted heteroaryl.
The layer that comprises sulfonamide (being total to) polymer may further include additional hydrophobic binder such as phenolic resins (phenolic novolac for example; Resol or polyvinyl phenol), chemical modification phenolic resins or contain the polymer of carboxyl, itrile group or maleimide base group.
The solubility behavior of coating can be regulated component through optional solubility and finely tune.More particularly, can use development accelerant and development restrainer.Coating comprises that these compositions can be added to the ground floor of this coating, in the second layer and/or optional other layer in the embodiment more than one layer therein.
Development accelerant is the compound as dissolution accelerator, because they can improve the rate of dissolution of coating.For example can use cyclic acid anhydride, phenols or organic acid are so that improve water-based development property.The example of cyclic acid anhydride comprises phthalic anhydride, tetrabydrophthalic anhydride, hexahydrophthalic anhydride, 3; 6-bridging oxygen-4-tetrahydrochysene-phthalic anhydride, tetrachlorophthalic tetrachlorophthalic anhydrid, maleic anhydride, chlorine maleic anhydride; α-phenyl maleic anhydride, succinyl oxide, and PMA; As at United States Patent(USP) No. 4,115, described in 128.The example of phenols comprises bisphenol-A, and is right-nitrophenols, right-ethyoxyl phenol, 2,4, and 4 '-trihydroxybenzophenone; 2,3,4-trihydroxybenzophenone, 4-dihydroxy benaophenonel, 4; 4 ', 4 "-and trihydroxy triphenyl methane and 4,4 ', 3 "; 4 "-tetrahydroxy-3,5,3 ', 5 '-tetramethyl triphenyl-methane, or the like.The organic acid example comprises sulfonic acid, sulfinic acid, and alkylsurfuric acid, phosphonic acids, phosphate, and carboxylic acids, according at for example JP-A No 60-88,942 and 2-96, described in 755.These organic acid specific examples comprise right-toluenesulfonic acid, and DBSA is right-toluenesulfinic acid, ethyl sulfuric acid, phenyl-phosphonic acid, phenyl phosphinic acid (phenylphosphinic acid); Phenyl phosphate, the di(2-ethylhexyl)phosphate phenylester, benzoic acid, M-phthalic acid, adipic acid, right-toluic acid; 3,4-dimethoxybenzoic acid, 3,4,5-trimethoxybenzoic acid, 3; 4,5-trimethoxy cinnamic acid, phthalic acid, terephthalic acid (TPA), 4-cyclohexene-1; The 2-dicarboxylic acids, sinapic acid, laurate, n-undecane acid, and ascorbic acid.In cyclic acid anhydride contained in the coating, phenol or organic acid amount preferably in 0.05-20wt% scope for whole coating.Comprise at least between 70mol%-cresols also is suitable development accelerant as the polymer development accelerant such as the phenolic resins of repeated monomer unit.
In preferred embodiments, this coating also contains developer opposing instrument (developerresistance means), is also referred to as development restrainer, promptly can in processing procedure, postpone not one or more compositions of the dissolving of exposed areas.The dissolving inhibitory action preferably reverses through heating, so that the dissolving of exposed areas does not postpone and therefore can obtain exposing to the open air and the big dissolving difference between the exposed areas not basically.Be described in EP-A for example 823 327 and be considered to can be used as dissolution inhibitor with compound among the WO97/39894, this owing to and coating in interaction (for example forming) between the alkali soluble resins through hydrogen bridge (hydrogen bridge).The inhibitor of this type comprises typically that at least one hydrogen bridge forms and uses group, like nitrogen-atoms, and base, (CO-), sulfinyl is (SO-) or sulfonyl (SO for carbonyl 2-) group and big hydrophobic structure part as one or more aromatic rings.Below in the mentioned compound some, for example IR dyes such as cyanines and contrast dyestuff (contrast dye) also can be used as dissolution inhibitor like quaternized triarylmethane dye.
Other suitable inhibitor improves the developer resistance, is penetrated into coating because they postpone aqueous alkaline developer.This compounds according to for example can be present in described in the EP-A 950 518 in the ground floor and/or; If exist; Be present in the second layer; And/or according at for example EP-A 864 420, EP-A 950 517, and WO 99/21725 is present in the development barrier layer on this layer with described in the WO 01/45958.In a back embodiment, the solubility of barrier layer or developer can be through being exposed to heat or infrared light improves to the permeability of barrier layer in developer.
The preferred example that the delay aqueous alkaline developer is penetrated into the inhibitor in the coating comprises following material:
(a) be insoluble to the polymeric material that maybe can't be developed agent infiltration in the developer, for example hydrophobicity and water repellency polymer or copolymer, like acrylic polymer, polystyrene; Styrene-propene acid based copolymer, polyester, polyamide; Polyureas, polyurethane, NC Nitroncellulose and epoxy resin; Or comprise the polymer of siloxanes (polysiloxanes) and/or perfluoroalkyl unit.
(b) dual functional compound, as comprise polar group and hydrophobic group such as long chain hydrocarbon groups, gather or the surfactant of oligosiloxane and/or perfluorinate alkyl.Typical example is Megafac F-177, can be from Dainippon Ink & Chemicals, the perfluorinate surfactant that Inc is purchased.The appropriate amount of this compounds is at 10-100mg/m 2Between, more preferably at 50-90mg/m 2Between.
(c) comprise the difunctionality block copolymer of polar block such as polymerization or oligomeric (alkylene oxide) (alkylene oxide) and hydrophobicity block such as long chain hydrocarbon groups, polymerization or oligosiloxane and/or perfluorinate alkyl.The appropriate amount of this compounds is at 0.5-25mg/m 2, preferably at 0.5-15mg/m 2Most preferably at 0.5-10mg/m 2Between.Suitable copolymers comprises about 15 to 25 siloxane units and 50 to 70 alkylen groups.Preferred example comprises the copolymer that comprises phenyl methyl siloxanes and/or dimethyl siloxane and oxirane and/or expoxy propane; Like Tego Glide 410; Tego Wet 265, Tego Protect 5001 or SilikophenP50/X all can be from Tego Chemie; Essen, Germany is purchased.This polymerization or oligosiloxane can be linear, ring-type or complex cross-linked polymer or copolymer.This term silicone compound should comprise any compound of siloxane group-Si (R, R ')-O-that contains more than, and wherein R and R ' are optional substituted alkyl or aryls.Preferred siloxanes is phenylalkyl siloxanes and dialkylsiloxane.The quantity of siloxane group is at least 2 in polymer or oligomer, preferably at least 10, more preferably at least 20.It can be lower than 100, preferably is lower than 60.
Can believe in coating and dry run; Even when as the composition of the coating solution of the ground floor and/or the optional second layer, (b) tend to itself be positioned at the interface between coating and the air because of their bifunctional structure and so form independent top layer with (c) the above-mentioned inhibitor of type.Simultaneously, this surfactant is also as the spreader-sticker that improves coating quality.As if formed independent top layer can be used as above-mentioned barrier layer, and it postpones developer and is penetrated in the coating.
Additionally, (a) inhibitor to (c) type can apply with independent solution, is coated in the ground floor of coating, on the optional second layer and/or the surface of other layer.In this embodiment, advantageously in this independent solution that can not be dissolved in those compositions that exist in other layer, use solvent, thereby on the surface of coating, obtain highly concentrated water repellency or hydrophobicity phase, the latter can be used as above-mentioned development barrier layer.
In addition, the ground floor or the optional second layer and/or other layer run length (run length) that can comprise further improvement galley and/or the polymer of chemical-resistant.Its example be comprise acylimino (CO-NR-CO-) polymer of side group, wherein R is a hydrogen, optional substituted alkyl or optional substituted aryl, as be described in EP-A 894 622, EP-A 901902, the polymer among EP-A 933 682 and the WO 99/63407.
The coating of the plate precursor of temperature-sensitive preferably also contains infrared Absorption property dyestuff or pigment; Coating comprises more than this dyestuff or pigment in the embodiment of one deck and can be present in ground floor therein; And/or be present in the second layer, and/or be present in other optional layer.Preferred IR absorbability dyestuff is a cyanine dyes, portion's cyanine dye (merocyanine dye), indoaniline dyes (indoaniline dye), oxonol dye, pyrans (pyrilium) dyestuff and side's acid (squarilium) dyestuff.The example of suitable IR dyestuff is described in for example EP-As823327,978376,1029667,1053868,1093934; Among the WO 97/39894 and 00/29214.Preferred compound is following cyanine dyes:
Figure GPA00001088352000251
Figure GPA00001088352000252
IR-1
For whole coating, in coating the concentration of IR dyestuff preferably 0.25 and 15.0%wt between, more preferably 0.5 and 10.0%wt between, most preferably 1.0 and 7.5%wt between.
Coating possibly further comprise one or more colouring agents, as perceived color being provided for coating and being retained in dyestuff or the pigment among the coating in the image-region that is not removed in the treatment step.Therefore formed visual picture, and the procuratorial work of the lithographic image on development galley becomes possibility.This type of dyestuff usually is known as contrast dyestuff or indicator dye.Preferably, this dyestuff has the maximum absorbance in blueness and the wave-length coverage between 600nm and 750nm.The exemplary of this type of contrast dyestuff is amino-substituted three-or triarylmethane colouring matters, crystal violet for example, and crystal violet, Victoria's ethereal blue, flexoblau 630, and basonylblau 640, yellow (auramine) and the peacock green (malachite green) of Chinese scholartree.The dyestuff of in EP 400 706, thoroughly discussing in addition is suitable contrast dyestuff.In for example only painted slightly this coating but become strong painted dyestuff after exposing to the open air and also can be used as colouring agent of combining with specific additive described in the WO2006/005688.
For the surface of the coating of protecting temperature-sensitive and/or photosensitive printing plate precursor, especially avoid mechanical damage, also can randomly apply protective layer.This protective layer generally includes at least a water-soluble binder, like polyvinyl alcohol, and polyvinylpyrrolidone; The polyvinyl acetate of partial hydrolysis; Gelatin, carbohydrate or hydroxyethylcellulose, and can be in any known fashion from aqueous solution or dispersion production; If necessary, it can contain on a small quantity-promptly the organic solvent that is lower than 5wt%-based on the gross weight of the paint solvent of protective layer.The thickness of protective layer can be any amount aptly, 5.0 μ m at the most advantageously, preferred 0.1 to 3.0 μ m, preferred especially 0.15 to 1.0 μ m.
Randomly, coating can further contain supplementary element such as other surfactant, and silicon or titanium dioxide granule or polymer beads are like delustering agent and interval dose (spacer).
Any painting method can be used in two or more coating solutions are applied on the hydrophilic surface of carrier.Laminated coating can apply through adjoining land/dry each layer or apply through several kinds of disposable coatings simultaneously of coating solution.In drying steps, this volatile solvent is removed from coating, until coating be self-supporting (self-supporting) and be dried to tangible till.Yet do not need (with perhaps even not possible) in drying steps, to remove whole solvents.In fact this residual solvent content can be thought the composition variable that adds, can optimize by means of its this composition.Drying is typically carried out through hot-air is blown on the coating, typically under at least 70 ℃ temperature, and 80-150 ℃ and especially 90-140 ℃ aptly.Also can use infrared lamp.Typically be 15-600 second drying time.
Apply and drying between, or after drying steps, heat treatment and follow-up cooling can provide additional benefit, as at WO99/21715; EP-A 1074386, EP-A1074889, WO00/29214; And WO/04030923, WO/04030924 is described in the WO/04030925.
The carrier of Lighographic printing plate precursor can be that flaky material such as plate or it can be cylindrical elements such as sleeve, and the latter can slide in that the printing cylinder of printing machine is peripheral.Preferably, carrier is metallic carrier such as aluminium or stainless steel.This carrier also can be the laminate that comprises aluminium foil and plastic layer such as polyester film.
Preferred especially lithographic support is with electrochemical process surface micro granulation and anodized alumina supporter.This alumina supporter has the thickness of about 0.1-0.6mm usually.Yet this thickness can come suitably to change according to the size of employed galley and/or the size of the integrated machine of forme (platesetter) (plate precursor is exposed to the open air above that).This aluminium preferably carries out the surface micro granulation and carries out anodization through the anodization technology that adopts phosphoric acid or sulfuric acid/phosphate mixture through the electrochemistry micronisation process.The micronize of aluminium and anodized method are well-known in the prior art.
Through with alumina supporter micronize (or roughening), the cohesive of printed images and the wetting characteristics of non-image areas all are improved.Through changing electrolytical type and/or concentration and in the micronize step, applying voltage, can obtain dissimilar particulates.Surface roughness usually is represented as arithmetic average center line roughness Ra (ISO 4287/1 or DIN 4762) and can between 0.05 and 1.5 μ m, changes.Aluminium base of the present invention preferably has and is lower than 0.45 μ m, more preferably less than 0.40 μ m with most preferably be lower than the Ra value of 0.30 μ m.The preferably about 0.1 μ m of the lower limit of Ra value.The more details of preferred Ra value that relate to the surface of micronize and anodized aluminum (anodized aluminum) carrier are described among the EP 1 356 926.
Through with the alumina supporter anodization, its wearability and hydrophily are improved.Al 2O 3The microtexture of layer and thickness are by the decision of anodization step, and anode weight (the anodicweight) (g/m that on the aluminium surface, forms 2Al 2O 3) can be at 1-8g/m 2Between change.Anode weight preferably>=3g/m 2, more preferably>=3.5g/m 2Most preferably>=4.0g/m 2
This micronize and anode alumina supporter can carry out the hydrophilic nmature of so-called back anode treatment with the surface of improving it.For example, this alumina supporter can through with sodium silicate solution in for example 95 ℃ of its surface of processing and silicic acid salinization down of the temperature that raises.Additionally, can adopt phosphate treated, it comprises with the phosphate solution that further contains inorganic fluoride handles alumina surface.In addition, this alumina surface can be with citric acid or citrate solution rinsing.This processing can at room temperature be carried out or can under about 30 ℃ to 50 ℃ temperature that raises a little, carry out.Other significant processing comprises with bicarbonate solution rinsing alumina surface.Further; This alumina surface can be used the polyvinyl phosphonic acids, polyvinyl methylphosphonic acid, polyethylene alcohol phosphate; Polyvinylsulfonic acid; Polystyrolsulfon acid (polyvinylbenzenesulphonic acid), the sulfuric ester of polyvinyl alcohol, and polyvinyl alcohol is through handling with the formed acetal of sulfonated aliphatic aldehyde reaction.
Another kind of useful back anode treatment can or comprise at least that the solution of the polymer of the acrylic monomers unit of 30mol% carries out with polyacrylic acid, the polyacrylic acid GLASCOL E15 that this polymer for example can be purchased from CibaSpeciality Chemicals.
This carrier also can be a flexible carrier, and it can the possess hydrophilic property layer, is called ' basal layer ' below.This flexible carrier for example is paper, plastic foil or aluminium.The preferred embodiment of plastic foil is the PETG film, poly (ethylene naphthalate) film, and cellulose acetate membrane, polystyrene film, polycarbonate membrane, or the like.Plastic film support can be opaque or transparent.
Basal layer is preferably from curing agent such as formaldehyde, glyoxal, the crosslinking hydrophilic property layer that polyisocyanates or the agent of hydrolysis orthosilicic acid tetraalkyl ester cross-linked hydrophilic cohesive obtain.The latter is preferred especially.The thickness of hydrophily basal layer can be in the 0.2-25 mu m range and 1-10 μ m preferably.The more details of the preferred embodiment of basal layer can for example find among the EP-A 1 025 992.
The plate precursor of this temperature-sensitive can directly utilize heat for example by means of thermal print head, or exposes to the open air with image mode through infrared light (preferred near infrared light) indirectly.This infrared light preferably utilizes IR light-absorbing compound previously discussed to be converted to heat.The Lighographic printing plate precursor of temperature-sensitive is preferably insensitive to visible light, does not promptly induce the big influence for the rate of dissolution of coating in developer through being exposed to visible light.Most preferably, coating is insensitive to environment daylight.
Plate precursor can be exposed to infrared light by means of for example LED or laser.Most preferably, the used about 1500nm that only has that makes public at about 750-, the more preferably near infrared light of the laser instrument of the wavelength in 750-1100nm scope emission, this laser instrument is semiconductor laser diode for example, Nd:YAG or Nd:YLF laser instrument.Required laser power depends on the sensitiveness of plate precursor, and the pixel time of staying of laser beam, (it was (at the 1/e of maximum intensity by spot diameter 2Under the representative value of the integrated machine of modern forme: decision 5-25 μ m)), (that is, the air line distance of the quantity/per unit of addressable pixel is usually expressed with dots per inch or dpi for the sweep speed of exposure device and resolution ratio; Representative value: 1000-4000dpi).
Usually use two types laser explosure device: inner (ITD) and the integrated machine of outside drum-type (XTD) forme.The integrated machine of ITD forme of temperature-sensitive version typically embodies characteristic in up to the very high sweep speed of 500m/ second and can need several watts laser power.Having about 200wW for example operates under 0.1 to 10m/sec in lower sweep speed to the integrated machine of XTD forme of the temperature-sensitive version of the typical laser power of about 1W.Be equipped be transmitted in 750 with the 850nm wave-length coverage in the integrated machine of XTD forme of one or more laser diodes of light be the especially preferred embodiment of method of the present invention.
Enough off line (off-press) exposure devices of doing of the integrated function of known forme, it provides the benefit that reduces printing downtime (press down-time).XTD forme integrated mechanism type also can be used in online (on-press) exposure, and the benefit of instant registration is provided in multicolour press.More ins and outs of online exposure device are described in for example US 5,174,205 and US5, in 163,368.
After exposure, this precursor preferably develops through this precursor is immersed in the developer solution; This can combine with mechanical friction, for example through using rotating brush.Remove at the preferred use alkaline development of the non-image areas of developing process floating coat agent solution.This developer solution preferably has more than 10, more preferably in the pH value more than 12.In development step, preferably also remove existing any water miscible coating.Under the temperature of 20 ℃ and 40 ℃ scopes, carry out in the process equipment of the preferred automation commonly used in the prior art of development step.
The more details that relate to development step can be at for example EP 1614538, and EP1614539 finds among EP 1614540 and the WO/2004071767.
This developing solution preferably contains buffer for example silicate-base buffer or phosphate buffer.The concentration of buffer is preferably between 3-14wt% in developer.Silicate-base developer with ratio of at least 1 silica and alkali metal oxide is desirable, because they guarantee that the alumina layer (if existence) of base material is injury-free.Preferred alkali metal oxide comprises Na 2O and K 2O and their mixture.Preferred especially silicate-base developer solution is the developer solution that comprises sodium or potassium metal silicate, and promptly wherein the ratio of silica and alkali metal oxide is 1 silicate.
This developer solution can be chosen wantonly and contain other component well known in the prior art: other buffer substance, chelating agent, surfactant; Compound, inorganic salts, inorganic alkaline agent; The organic basic agent, antifoaming agent promptly preferably is lower than on a small quantity 10%wt and more preferably less than the organic solvent of 5%wt; Nonreducing sugar, glucosides, dyestuff and/or hydrotropic solvent.The use of can using separately or combine of these components.
The stable processing with developer solution in order to ensure the longer time it is especially important the concentration that is controlled at various compositions in the developer.Therefore make-up solution (replenishingsolution) (below be also referred to as replenishers) usually is added in the developer.Contain can being added in this developer solution of heterogeneity and/or the different compositions of measuring more than a kind of make-up solution.Suitable use has the alkali metal silicate solutions of the alkali metal content of 0.6-2.0mol/l.These solution have the silica/alkali metal oxide ratio identical with developer (yet usually, it is lower) and likewise optional other additive that contains.It is desirable to, (being total to) of the present invention polymer is present in the replenishers; Preferably with the concentration of 0.5g/l at least, more preferably to exist with the concentration between the 2-30g/l between the 1-50g/l and most preferably.
This make-up solution preferably has at least 10, and more preferably at least 11, at least 12 pH value most preferably.
After this development step, be rinse step, gluing (gumming) step, drying steps and/or back baking step.
The galley of this temperature-sensitive can be used in common, so-called wet hectographic printing, and wherein printing ink and water-based are soaked liquid and be supplied to this galley.The so-called single fluid printing ink (single-fluid ink) that does not soak liquid is used in another suitable printing process.Suitable single fluid printing ink has been described in US 4,045,232; US 4,981,517 with US 6,140,392 in.In most preferred embodiment, single fluid printing ink comprises the printing ink phase, is also referred to as hydrophobicity or lipophile phase, with polyalcohol mutually, as described in the WO 00/32705.
Plate precursor of the present invention also can be used in handles the thermic resist, for example in PCB (printed circuit board (PCB)) application, as described in US 2003/0003406 A1.
Embodiment
1. the preparation of lithographic support.
0.30mm the thickness aluminium foil is through this paper tinsel being immersed in 70 ℃ the aqueous solution of the NaOH that contains 34g/l 6 seconds, uses demineralized water rinsing 3.6 seconds then and degreasing.This paper tinsel is then at 37 ℃ temperature and 100A/dm 2Current density under through containing 15g/l HCl, 15g/l SO 4 2-Ion and 5g/l Al 3+Aqueous solution in use alternating current in 8 seconds time, to carry out the electrochemistry micronize.This aluminium foil then through with the aqueous solution of sulfuric acid that contains 145g/l 80 ℃ of following etchings 5 seconds with removed stain (desmut) in 4 seconds with the demineralized water rinsing then.This paper tinsel subsequently in the aqueous solution of the sulfuric acid that contains 145g/l at 57 ℃ temperature and 25A/dm 2Current density under in 10 seconds process, carry out anodic oxidation, then with demineralized water washing 7 seconds and with the solution of the polyvinyl phosphonic acids that contains 2.2g/l 70 ℃ of following post processings 4 seconds, with demineralized water rinsing 3.5 seconds with 120 ℃ times dryings 7 seconds.
The carrier that is obtained embodies surface roughness Ra and the 3.0g/m of characteristic in 0.35-0.40 μ m (measuring with interferometer NT1100) 2Anode weight.
2. plate precursor PPP-1 to PPP-16.
2.1. ground floor.
Go up coating ground floor with the wet coating layer thickness of 20 μ m at aluminium base (as stated) with first kind of coating solution with defined composition in the table 1.
Table 1: the composition of first kind of coating solution.
The composition of first kind of coating solution g
Dowanol?PM(1) 270.98
THF(2) 576.55
Binding agent-01 (25wt%) (3) 53.75
Crystal violet (1wt%) (4) 58.24
Tegoglide?410(1wt％)(5) 5.82
Propane diols-the monomethyl ether (1-methoxyl group-2-propyl alcohol) that (1) can be purchased from Dow Chemical Company;
(2) THF is an oxolane;
(3) binding agent-01: preparation is referring to 2.2;
(4) the 1wt% solution of crystal violet in Dowanol PM, crystal violet can be purchased from Ciba-Geigy GmbH;
(5) the 1wt% solution of Tegoglide 410 in Dowanol PM; Tegoglide410 is polysiloxanes and the copolymer that gathers (alkylene oxide), can be purchased from Tego Chemie ServiceGmbH.
The dry coating gross weight adds up to 0.671g/m 2The dry weight of various compositions is shown in table 2 in first coating.
Table 2: the dry coating weight of first coating
The dry weight * of first coating mg/m 2
Binding agent-01 660
Crystal violet 10
?Tegoglide?410 1
* the composition that in table 1, defines.
2.2. the preparation of binding agent-01.
In the 250ml reactor, add the monomer-01 (structure sees below) of 162mmol, 21.3g (132mmol) benzyl acrylamide, 0.43g (6mmol) acrylic acid and 103g gamma-butyrolacton, mixture is heated to 140 ℃ then, under 200rpm, stirs simultaneously.The nitrogen of constant flow rate passes through on reactor.After the dissolving of whole components, reactor is cooled to 100 ℃.Add 0.35ml Trigonox TMDC50 (can be purchased from AKZO NOBEL) will be dissolved in the 1.39ml Trigonox in the 3.43ml butyrolactone subsequently TM141 (can be purchased from AKZO NOBEL) add.The beginning polymerisation, reactor was heated to 140 ℃ through 2 hours, according to dosage added (dose) 1.75ml Trigonox simultaneously TMDC50.Mixture stirs under 400rpm, continues then under 140 ℃, to carry out polymerisation 2 hours.Reactant mixture is cooled to 120 ℃, and agitator speed is brought up to 500rpm then.Add 1-methoxyl group-2-propyl alcohol of 85.7ml, then the reactant mixture cool to room temperature.
Binding agent-01 usefulness 1H-NMR wave spectrum and SEC through using dimethylacetylamide/0.21%LiCl as eluant, eluent, are analyzed on 3x mixing-B post and with respect to polystyrene standards.
M n M w PD
Binding agent-01 23500 67000 2.84
Reactant mixture is cooled to 40 ℃ and is collected in the drum (drum) with resulting 25%wt polymer solution.
Monomer-01:
2.3. the second layer.
Second coating solution (coating solution 1-16) with defined composition in table 3 is that the wet coating layer thickness with 16 μ m is applied on the ground floor, obtains plate precursor PPP-01 to PPP-16.
Figure GPA00001088352000331
Figure GPA00001088352000341
1) Alnovol SPN402 is the 44.3wt% solution of novolac resin among Dowanol PM that can be purchased from Clariant GmbH.
2) the 10wt% solution of TMCA (3,4, the 5-trimethoxy cinnamic acid) in Dowanol PM.
3) Adagio is the IR absorbability cyanine dyes that can be purchased from FEWCHEMICALS with chemical constitution IR-1 (referring to top).
4) the 1wt% solution of crystal violet in Dowanol PM, crystal violet can be purchased from Ciba-Geigy GmbH.
5) the 1wt% solution of Tegoglide 410 in Dowanol PM; Polysiloxanes and the copolymer that gathers (alkylene oxide) can be purchased from Tego Chemie Service GmbH.
6) the 1wt% solution of PolyFox PF-636 in Dowanol PM can be purchased and contains the following chemical structure from Omnova Solutions Inc.:
Figure GPA00001088352000351
Have and equal about 6 number-average degree of polymerization t+u.
7) the wt% solution of PolyFox PF-6520 in Dowanol PM can be purchased and contains the following chemical structure from Omnova Solutions Inc.:
Figure GPA00001088352000352
Have and equal about 20 number-average degree of polymerization s+r.
8) the 1wt% solution of PolyFox PF-656 in Dowanol PM can be purchased and contains the following chemical structure from Omnova Solutions Inc.:
Figure GPA00001088352000361
Have and equal about 6 number-average degree of polymerization s+r.
9) the 1wt% solution of PolyFox PF-6320 in Dowanol PM can be purchased and contains the following chemical structure from Omnova Solutions Inc.:
Have and equal about 20 number-average degree of polymerization t+u.
10) the 1wt% solution of PolyFox PF-159N in Dowanol PM can be purchased and contains the following chemical structure from Omnova Solutions Inc.:
Figure GPA00001088352000363
11) the 1wt% solution of PolyFox PF-652 in Dowanol PM can be purchased as 50% solution isopropyl alcohol from Omnova Solutions Inc., and PolyFoxPF-652 contains the following chemical structure:
Figure GPA00001088352000371
Have number-average degree of polymerization x+y that equals about 10 and the number-average degree of polymerization p+q that equals about 17.8.
12) the 1wt% solution of PolyFox PF-651 in Dowanol PM can be purchased as 50% solution isopropyl alcohol from Omnova Solutions Inc., and PolyFoxPF-651 contains the following chemical structure:
Figure GPA00001088352000372
Have number-average degree of polymerization n that equals about 10 and the number-average degree of polymerization m that equals about 8.9.
The dry coating gross weight of second coating and their composition separately are shown in Table 4.
Table 4: the dry coating weight of second coating.
The dry weight * of second coating mg/m 2
Alnovol?SPN402 653.0
TMCA 56.0
Adagio 25.0
Crystal violet 10.0
Perfluorinated surface-active agent 5.0 or 10.0
Altogether: 749 or 754
*: the dry coating weight total no more than 744mg/m of second coating of PPP-01 2The composition of coating is stipulated in table 3.
3. plate precursor 1-16's exposes to the open air.
Plate precursor PPP-01 is to PPP-16 imaging under 140rpm and 2400dpi on the Creo TrendSetter with 40W imaging head (can be purchased from Kodak), then AgfaAutolith TP105 processor (can be purchased) from Agfa Graphics NV with Agfa EnergyElite developer (can from Agfa Graphics NV, be purchased) (23 ℃ of temperature, 25 seconds time of staying) and in finished product (finisher) section, develop in the developer section with running water (room temperature).
4. the evaluation of plate precursor 1-16.
4.1. the evaluation of coefficient of friction.
Measure the static friction coefficient of preceding surface.The value of needs at least 0.45 is to prevent that these galleys obtain " scratch " defective in the generation of displacement each other in transportation.
With standard A STM D 1894 on-line measurement static friction coefficients.Use following experimental rig:
Figure GPA00001088352000381
Wherein
A: the meter of measuring the frictional force between d and g;
B: pulley;
C: nylon wire;
D a: part (the Pleiderer Pergo-Tec 37g/m of typical intermediate layer paper 2);
E: stainless steel module;
F: carrier;
G: photosensitive layer is towards last plate precursor.
Static friction coefficient is defined as the weight of the peak power (N) of mobile stainless steel module e divided by the stainless steel module.
This evaluation is carried out 5 times in the plate precursor 1 to 16 each.The result of this evaluation (mean value and standard deviation) is shown in Table 5.
4.2. the evaluation of coating performance (outward appearance).
In order to estimate each fastness for coating and drying condition in second coating solution; It is coating performance; Use to be described in each among the coating solution 1-16 in 2.3, but through using very strict drying condition to carry out 1 time described additional coated test on alumina supporter:
-step 1: drying is 30 seconds under the condition that is described below;
-step 2: following dry 3 minutes at 135 ℃ in hot-air (convection current) baking oven.
Employed drying condition in step 1:
Figure GPA00001088352000391
Wherein
A is at 2 grades of hair-dryers (WIGO Taifun110ch, 1000W power can be purchased from WIGO) that use down of the highest available blowing ability.
B is a plate precursor.
After coating and the drying, the precursor that is obtained carries out visual evaluation through qualitative scale below using with regard to coating uniformity under aforesaid condition:
The strong muddy coating of 1=
The muddy coating of 2=
The muddy a little coating of 3=
4=is uniform coating almost
The excellent uniform coating of 5=
In order under industrial condition, to apply layer, need at least 4 value of outward appearance or the coating performance on surface with enough scopes (latitude).
4.3. correctly expose the evaluation of sensitiveness to the open air.
Correctly exposing (RE) sensitiveness to the open air is energy density values (mJ/cm 2), wherein after processing on galley 1 * 1 checkerboard pattern reading 52% (Gretag-MacBeth D19C densitometer, automatic colour filter setting).
Correctly expose sensitiveness (RE) to the open air, the result of ocular estimate level/coating performance and coefficient of friction evaluation is shown in Table 5.
Table 5: static friction coefficient and sensitiveness result.
Plate precursor " RE " sensitiveness (mJ/cm 2) Static friction coefficient * Appearance of coat * * Dry coating weight (the mg/m of surfactant 2)
PPP 1; Reference 111 0.60±0.008 2 -
PPP 2; Contrast 109 0.16±0.009 5 5.0
PPP 3; Contrast na na 1 5.0
PPP 4; Contrast na na 1 10.0
PPP 5; Contrast 98 0.36±0.019 4 5.0
PPP 6; Contrast 84 0.31±0.010 4.5 10.0
PPP 7; Contrast na na 3 5.0
PPP 8; Contrast na na 3 10.0
PPP 9; Contrast 83 0.46±0.023 1 5.0
PPP 10; Contrast 101 0.33±0.016 1 10.0
PPP 11; Contrast na na 1 5.0
PPP 12; Contrast na na 1 10.0
PPP 13; The present invention 97 0.58±0.002 5 5.0
PPP 14; The present invention 88 0.57±0.004 4 10.0
PPP 15; The present invention 108 0.56±0.008 4.5 5.0
PPP 16; The present invention 99 0.48±0.008 4 10.0
Na=can't obtain data;
* measure as stated;
* uses following qualitative scale to come the visual evaluation coating uniformity:
The strong muddy coating of 1=
The muddy coating of 2=
The muddy a little coating of 3=
4=is uniform coating almost
The excellent uniform coating of 5=.
The result of table 5 shows, contrast galley has poor coating performance result (being the appearance of coat level of 1-3), or when coating performance was acceptable i.e. at least 4 appearance of coat level, static friction system was not sufficiently high (being lower than 0.45).
Comprise surfactant PolyFox PF-652 and PolyFox PF-651, the plate precursor of the present invention of PPP-13 to PPP-16 allow at least 4 the appearance of coat evaluation level of good coating performance-promptly-with at least 0.45 the static friction coefficient of sufficiently high static friction coefficient-is promptly arranged simultaneously.PolyFox PF-652 has supplementary features, and promptly it is presented at performance very consistent in the employed concentration range.
These sensitiveness result compares for whole plate precursor PPP-1 to PPP-16.

Claims (30)

1. the positivity Lighographic printing plate precursor of temperature-sensitive; It is included in temperature-sensitive that comprises surfactant and/or photosensitive coating on micronize and the anodized aluminum carrier; This carrier possess hydrophilic property surface or possess hydrophilic layer and have the surface roughness that is expressed as arithmetic average center line roughness Ra between 0.05-1.5 μ m is characterized in that this surfactant comprises the polyether block that comprises fluothane side group and urethane linking group.
2. according to the plate precursor of claim 1, wherein this surface roughness Ra is to be lower than 0.45 μ m.
3. according to the plate precursor of claim 1, wherein this carrier has at 1-8g/m 2Between anode weight.
4. according to the plate precursor of claim 3, wherein this carrier has>=3g/m 2Anode weight.
5. according to the plate precursor of claim 1, wherein this fluothane side group is the alkoxyl fluoroalkyl.
6. according to the plate precursor of claim 5, wherein this surfactant comprises the structure unit:
Wherein
A and b represent independently >=0 integer;
C representes 1 to 40 integer;
Y 1Expression fluoroalkyl or alkoxyl fluoroalkyl;
Y 2Expression hydrogen, optional substituted alkyl, fluoroalkyl or alkoxyl fluoroalkyl;
R 1To R 4Represent hydrogen independently, fluoride, fluoroalkyl, optional substituted alkyl or optional substituted aryl.
7. according to the precursor of claim 6, wherein this surfactant comprises the structure unit:
Figure FSB00000662167100021
Wherein d and e represent >=1 integer;
X representes fluoroalkyl;
Y 3Expression hydrogen or optional substituted alkyl;
And f is illustrated in the integer between 1 and 40.
8. according to the plate precursor of claim 1, wherein this surfactant further comprises the structure unit:
Figure FSB00000662167100022
R wherein 5Expression hydrogen; Optional substituted alkyl or optional substituted aryl, aralkyl or assorted alkyl;
And k is illustrated in the integer between 1 and 40.
9. according to the plate precursor of claim 1, wherein this surfactant comprises the structure unit:
Figure FSB00000662167100023
And/or
Figure FSB00000662167100031
The m in each in these compounds wherein, n, o and p are illustrated in the integer between 1 and 40 independently.
10. according to the plate precursor of claim 1, wherein surfactant is a kind of in the following compounds:
Figure FSB00000662167100041
The m in each in these compounds wherein, n, o, p, x, y, q and v are illustrated in the integer between 1 and 40 independently.
11. according to the plate precursor of claim 4, wherein surfactant comprises the structure unit:
Figure FSB00000662167100042
And/or
Figure FSB00000662167100043
The m in each in these compounds wherein, n, o and p are illustrated in the integer between 1 and 40 independently.
12. according to the plate precursor of claim 4, wherein this surfactant is a kind of in the following compounds:
Figure FSB00000662167100051
Figure FSB00000662167100061
The m in each in these compounds wherein, n, o, p, x, y, q and v are illustrated in the integer between 1 and 40 independently.
13. according to any one plate precursor in the aforementioned claim, wherein this surfactant is to be present in this coating with the amount between 0.05%wt and the 5%wt.
14. according to any one plate precursor among the aforementioned claim 1-10, wherein this surfactant is to be present in this coating with the amount between 0.1%wt and the 3%wt.
15. according to any one plate precursor among the aforementioned claim 1-10, wherein this surfactant is to be present in this coating with the amount between 0.15%wt and the 1.5%wt.
16. according to the plate precursor of claim 1, wherein this coating comprises at least two layers
-comprise the layer of lipophilic resin;
-comprising another layer of sulfonamide binding agent, it comprises between the layer of lipophilic resin at carrier and this;
Wherein this surfactant is present in the layer that comprises lipophilic resin.
17. according to the plate precursor of claim 16, wherein this sulfonamide binding agent is to be expressed from the next:
Wherein
R 9Represent hydrogen or have the alkyl of 12 carbon atoms at the most;
X 1Expression singly-bound or divalent linker;
Y 4It is the divalence sulfuryl amine group;
And Z 1The expression end group.
18. according to the plate precursor of claim 16, wherein this carrier has at 1-8g/m 2Between anode weight.
19. according to the plate precursor of claim 16, wherein this carrier has>=3g/m 2Anode weight.
20. according to the plate precursor of claim 16, wherein this fluoroalkyl is the alkoxyl fluoroalkyl.
21. according to the plate precursor of claim 20, wherein this surfactant comprises the structure unit:
Figure FSB00000662167100071
Wherein
A and b represent independently >=0 integer;
C representes 1 to 40 integer;
Y 1Expression fluoroalkyl or alkoxyl fluoroalkyl;
Y 2Expression hydrogen, optional substituted alkyl, fluoroalkyl or alkoxyl fluoroalkyl;
R 1To R 4Represent hydrogen independently, fluoride, fluoroalkyl, optional substituted alkyl or optional substituted aryl.
22. according to the precursor of claim 21, wherein this surfactant comprises the structure unit:
Figure FSB00000662167100072
Wherein d and e represent >=1 integer;
X representes fluoroalkyl;
Y 3Expression hydrogen or optional substituted alkyl;
And f is illustrated in the integer between 1 and 40.
23. according to the plate precursor of claim 16, wherein this surfactant further comprises the structure unit:
Figure FSB00000662167100081
R wherein 5Expression hydrogen; Optional substituted alkyl or optional substituted aryl, aralkyl or assorted alkyl;
And k is illustrated in the integer between 1 and 40.
24. according to the plate precursor of claim 16, wherein this surfactant comprises the structure unit:
Figure FSB00000662167100082
And/or
The m in each in these compounds wherein, n, o and p are illustrated in the integer between 1 and 40 independently.
25. according to the plate precursor of claim 16, wherein this surfactant is a kind of in the following compounds:
Figure FSB00000662167100091
Figure FSB00000662167100101
The m in each in these compounds wherein, n, o, p, x, y, q and v are illustrated in the integer between 1 and 40 independently.
26. according to any one plate precursor among the aforementioned claim 16-25, wherein this surfactant is to be present in this coating with the amount between 0.05%wt and the 5%wt.
27. according to any one plate precursor among the aforementioned claim 16-25, wherein this surfactant is to be present in this coating with the amount between 0.1%wt and the 3%wt.
28. according to any one plate precursor among the aforementioned claim 16-25, wherein this surfactant is to be present in this coating with the amount between 0.15%wt and the 1.5%wt.
29. make the method for Lighographic printing plate precursor, it may further comprise the steps
-apply according to defined coating in any one in the aforementioned claim;
-dry this precursor.
30. make the method for lithographic plate, it may further comprise the steps
-provide according to any one plate precursor in the aforementioned claim;
-this precursor is exposed to heat and/or infrared light;
-use alkaline solution develops this precursor that exposes to the open air.
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