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EP1396338A1 - Wärmeempfindlicher Flachdruckplattenvorläufer - Google Patents

Wärmeempfindlicher Flachdruckplattenvorläufer Download PDF

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Publication number
EP1396338A1
EP1396338A1 EP02102303A EP02102303A EP1396338A1 EP 1396338 A1 EP1396338 A1 EP 1396338A1 EP 02102303 A EP02102303 A EP 02102303A EP 02102303 A EP02102303 A EP 02102303A EP 1396338 A1 EP1396338 A1 EP 1396338A1
Authority
EP
European Patent Office
Prior art keywords
group
printing plate
plate precursor
coating
precursor according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP02102303A
Other languages
English (en)
French (fr)
Other versions
EP1396338B1 (de
Inventor
Geert Deroover
Marc Van Damme
Joan Vermeersch
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Agfa NV
Original Assignee
Agfa Gevaert NV
Agfa Gevaert AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Agfa Gevaert NV, Agfa Gevaert AG filed Critical Agfa Gevaert NV
Priority to EP20020102303 priority Critical patent/EP1396338B1/de
Priority to DE2002613236 priority patent/DE60213236T2/de
Priority to JP2003310344A priority patent/JP2004102279A/ja
Priority to US10/654,508 priority patent/US20040048195A1/en
Publication of EP1396338A1 publication Critical patent/EP1396338A1/de
Application granted granted Critical
Publication of EP1396338B1 publication Critical patent/EP1396338B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • B41C2201/14—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
    • B41C2210/262—Phenolic condensation polymers, e.g. novolacs, resols
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/46—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography characterised by the light-to-heat converting means; characterised by the heat or radiation filtering or absorbing means or layers
    • B41M5/465—Infrared radiation-absorbing materials, e.g. dyes, metals, silicates, C black

Definitions

  • the present invention relates to a heat-sensitive lithographic printing plate precursor that requires aqueous alkaline processing.
  • Lithographic printing typically involves the use of a so-called printing master such as a printing plate which is mounted on a cylinder of a rotary printing press.
  • the master carries a lithographic image on its surface and a print is obtained by applying ink to said image and then transferring the ink from the master onto a receiver material, which is typically paper.
  • ink as well as an aqueous fountain solution also called dampening liquid
  • dampening liquid are supplied to the lithographic image which consists of oleophilic (or hydrophobic, i.e. ink-accepting, water-repelling) areas as well as hydrophilic (or oleophobic, i.e. water-accepting, ink-repelling) areas.
  • driographic printing the lithographic image consists of ink-accepting and ink-abhesive (ink-repelling) areas and during driographic printing, only ink is supplied to the master.
  • Printing masters are generally obtained by the so-called computer-to-film method wherein various pre-press steps such as typeface selection, scanning, color separation, screening, trapping, layout and imposition are accomplished digitally and each color selection is transferred to graphic arts film using an image-setter.
  • the film can be used as a mask for the exposure of an imaging material called plate precursor and after plate processing, a printing plate is obtained which can be used as a master.
  • a typical photosensitive printing plate precursor for computer-to-film methods comprises a hydrophilic support and an image-recording layer which includes UV-sensitive compositions.
  • a negative-working plate typically by means of a film mask in a UV contact frame
  • the exposed image areas become insoluble and the unexposed areas remain soluble in an aqueous alkaline developer.
  • the plate is then processed with the developer to remove the diazonium salt or diazo resin in the unexposed areas. So the exposed areas define the image areas (printing areas) of the printing master, and such printing plate precursors are therefore called 'negative-working'.
  • positive-working materials wherein the exposed areas define the non-printing areas, are known, e.g. plates having a novolac/naphtoquinone-diazide coating which dissolves in the developer only at exposed areas.
  • heat-sensitive printing plate precursors have become very popular.
  • thermal materials offer the advantage of daylight-stability and are especially used in the so-called computer-to-plate method wherein the plate precursor is directly exposed, i.e. without the use of a film mask.
  • the material is image-wise exposed to heat or to infrared laser light and the generated heat triggers a (physico-)chemical process, such as ablation, polymerization, insolubilization by cross-linking of a polymer or by particle coagulation of a thermoplastic polymer latex, and solubilization by the destruction of intermolecular interactions.
  • the coating of a typical heat-sensitive lithographic printing plate precursor which requires alkaline processing contains an alkali-soluble binder and an infrared light absorbing compound, which converts infrared light into heat.
  • the light-to-heat converting compound is typically an organic dye, often a cyanine dye, which acts as a dissolution inhibitor on the binder, i.e. it increases the resistance of the coating towards the alkaline developer and thereby reduces the sensitivity of the coating. As a result, a high light power or a longer exposure time is required during the image-wise exposure.
  • WO97/39894 and EP-A 823327 disclose examples of such inhibiting dyes.
  • EP-A 978376 discloses that infrared cyanine dyes having a betaine structure do not reduce the solubility of the coating in the developer. These dyes, however, are not readily soluble in an alkaline developer and tend to cause dye stain at non-image areas of the printing plate.
  • the cyanine dyes which are defined in claim 1 comprise a bridged methine chain and three, four or five solubilizing groups. Dyes having less than three solubilizing groups do not provide the combined advantage of high speed and low stain, whereas dyes having more than five solubilizing groups tend to precipitate by crystallization from the coating solution or from the coated layer during the drying step.
  • the heat-sensitive lithographic printing plate precursor of the present invention contains a hydrophilic support and a coating comprising an oleophilic layer provided thereon. Besides the oleophilic layer, the coating may also comprise one or more additional layer(s) of which examples are discussed below.
  • the coating contains, in the oleophilic layer and/or in any of said additional layers, an infrared light absorbing compound according to the following formula I : wherein
  • G 1 and G 2 are solubilizing groups, i.e. groups which are anionic or which become anionic in an aqueous alkaline solution having a pH of at least 9, preferably at least 12.
  • the total number of solubilizing groups G 1 and G 2 is equal to three, four or five.
  • Suitable examples of such solubilizing groups are -COOH, -OH, -PO 3 H 2 , -O-PO 3 H 2 , -SO 3 H, -O-SO 3 H, -SO 2 -NH 2 , -SO 2 -NH-R, -SO 2 -NH-CO-R, or the salts of any of these groups, e.g.
  • R is an optionally substituted alkyl, alkenyl, aryl or aralkyl group.
  • the most preferred embodiments are -COOH, -SO 3 H, and - OH.
  • the concentration of the IR absorbing compound in the coating is typically between 0.25 and 10.0 wt.%, more preferably between 0.5 and 7.5 wt.%, relative to all non-volatile ingredients of the coating.
  • Suitable subclasses of the above dyes are represented by the following formulae :
  • m, n, R 1 , R 2 , R 3 , R 4 , R 5 , Z 1 , Z 2 and Z 3 have the same meaning as in formula I above.
  • Integer o has a value between 0 and 5.
  • R 10 represents a group as defined for R 4 and R 5 .
  • any of the above formula I to XVIII wherein such fused phenyl group is present also represent dyes that are suitable for a precursor of the present invention.
  • Two preferred embodiments of such dyes are represented by formula XIX and XX : wherein m, n, R 1 , R 2 , R 3 , Z 1 , Z 2 and Z 3 have the same meaning as in formula I above; p and q are independently 0, 1 or 2 and each R 6 to R 9 independently represents a group as defined for R 1 and R 2 above.
  • the above two configurations of fused phenyl groups are derivatives of formula I above. Similar derivatives can be constructed from any of the formula II to XVIII and such subclasses also are part of the present invention.
  • the formation of the lithographic image by the plate precursor of the present invention is due to a heat-induced solubility differential of the coating during processing in the developer.
  • the solubility differentiation between image (printing, oleophilic) and non-image (non-printing, hydrophilic) areas of the lithographic image is characterized by a kinetic rather than a thermodynamic effect, i.e. the non-image areas are characterized by a faster dissolution in the developer that the image-areas.
  • the non-image areas of the coating dissolve completely in the developer before the image areas are attacked so that the latter are characterized by sharp edges and high ink-acceptance.
  • the time difference between completion of the dissolution of the non-image areas and the onset of the dissolution of the image areas is preferably longer than 10 seconds, more preferably longer than 20 seconds and most preferably longer than 60 seconds, thereby offering a wide development latitude.
  • the precursor can be positive- or negative-working with the positive-working embodiment being preferred.
  • the support of the lithographic printing plate precursor has a hydrophilic surface or is provided with a hydrophilic layer.
  • the support may be a sheet-like material such as a plate or it may be a cylindrical element such as a sleeve which can be slid around a print cylinder of a printing press.
  • the support is a metal support such as aluminum or stainless steel.
  • the support can also be a laminate comprising an aluminum foil and a plastic layer, e.g. polyester film.
  • a particularly preferred lithographic support is an electrochemically grained and anodized aluminum support. Graining and anodization of aluminum is well known in the art.
  • the anodized aluminum support may be treated to improve the hydrophilic properties of its surface.
  • the aluminum support may be silicated by treating its surface with a sodium silicate solution at elevated temperature, e.g. 95°C.
  • a phosphate treatment may be applied which involves treating the aluminum oxide surface with a phosphate solution that may further contain an inorganic fluoride.
  • the aluminum oxide surface may be rinsed with a citric acid or citrate solution. This treatment may be carried out at room temperature or may be carried out at a slightly elevated temperature of about 30 to 50°C.
  • a further interesting treatment involves rinsing the aluminum oxide surface with a bicarbonate solution.
  • the aluminum oxide surface may be treated with polyvinylphosphonic acid, polyvinylmethylphosphonic acid, phosphoric acid esters of polyvinyl alcohol, polyvinylsulfonic acid, polyvinylbenzenesulfonic acid, sulfuric acid esters of polyvinyl alcohol, and acetals of polyvinyl alcohols formed by reaction with a sulfonated aliphatic aldehyde It is further evident that one or more of these post treatments may be carried out alone or in combination.
  • the support can also be a flexible support, which is provided with a hydrophilic layer, hereinafter called 'base layer'.
  • the flexible support is e.g. paper, plastic film, thin aluminum or a laminate thereof.
  • Preferred examples of plastic film are polyethylene terephthalate film, polyethylene naphthalate film, cellulose acetate film, polystyrene film, polycarbonate film, etc.
  • the plastic film support may be opaque or transparent.
  • the base layer is preferably a cross-linked hydrophilic layer obtained from a hydrophilic binder cross-linked with a hardening agent such as formaldehyde, glyoxal, polyisocyanate or a hydrolyzed tetra-alkylorthosilicate.
  • a hardening agent such as formaldehyde, glyoxal, polyisocyanate or a hydrolyzed tetra-alkylorthosilicate.
  • the thickness of the hydrophilic base layer may vary in the range of 0.2 to 25 ⁇ m and is preferably 1 to 10 ⁇ m.
  • the hydrophilic binder for use in the base layer is e.g.
  • hydrophilic (co)polymer such as homopolymers and copolymers of vinyl alcohol, acrylamide, methylol acrylamide, methylol methacrylamide, acrylate acid, methacrylate acid, hydroxyethyl acrylate, hydroxyethyl methacrylate or maleic anhydride/vinylmethylether copolymers.
  • the hydrophilicity of the (co)polymer or (co)polymer mixture used is preferably the same as or higher than the hydrophilicity of polyvinyl acetate hydrolyzed to at least an extent of 60% by weight, preferably 80% by weight.
  • the amount of hardening agent, in particular tetraalkyl orthosilicate, is preferably at least 0.2 parts per part by weight of hydrophilic binder, more preferably between 0.5 and 5 parts by weight, most preferably between 1 parts and 3 parts by weight.
  • the hydrophilic base layer may also contain substances that increase the mechanical strength and the porosity of the layer.
  • colloidal silica may be used.
  • the colloidal silica employed may be in the form of any commercially available water dispersion of colloidal silica for example having an average particle size up to 40 nm, e.g. 20 nm.
  • inert particles of larger size than the colloidal silica may be added e.g. silica prepared according to Stöber as described in J. Colloid and Interface Sci., Vol. 26, 1968, pages 62 to 69 or alumina particles or particles having an average diameter of at least 100 nm which are particles of titanium dioxide or other heavy metal oxides.
  • the surface of the hydrophilic base layer is given a uniform rough texture consisting of microscopic hills and valleys, which serve as storage places for water in background areas.
  • hydrophilic base layers for use in accordance with the present invention are disclosed in EP-A- 601 240, GB-P- 1 419 512, FR-P- 2 300 354, US-P- 3 971 660, and US-P- 4 284 705.
  • the oleophilic layer contains a polymer that is soluble in an aqueous alkaline developer.
  • Any organic, polymeric binder can be used in the present invention.
  • the organic, polymeric binder is preferably a binder having acidic groups with a pKa of less than 13 to ensure that the layer is soluble or at least swellable in aqueous alkaline developers.
  • the binder is a polymer or polycondensate, for example a polyester, polyamide, polyurethane or polyurea.
  • Polycondensates and polymers having free phenolic hydroxyl groups as obtained, for example, by reacting phenol, resorcinol, a cresol, a xylenol or a trimethylphenol with aldehydes, especially formaldehyde, or ketones are also particularly suitable.
  • Condensates of sulfamoyl- or carbamoyl-substituted aromatics and aldehydes or ketones are also suitable.
  • Polymers of bismethylol-substituted ureas, vinyl ethers, vinyl alcohols, vinyl acetals or vinylamides and polymers of phenylacrylates and copolymers of hydroxylphenylmaleimides are likewise suitable.
  • polymers having units of vinylaromatics, N-aryl(meth)acrylamides or aryl (meth)acrylates may be mentioned, it being possible for each of these units also to have one or more carboxyl groups, phenolic hydroxyl groups, sulfamoyl groups or carbamoyl groups.
  • Specific examples include polymers having units of 2-hydroxyphenyl (meth)acrylate, of N-(4-hydroxyphenyl)(meth)acrylamide, of N-(4-sulfamoylphenyl)-(meth)acrylamide, of N-(4-hydroxy-3,5-dimethylbenzyl)-(meth)acrylamide, or 4-hydroxystyrene or of hydroxyphenylmaleimide.
  • the polymers may additionally contain units of other monomers which have no acidic units.
  • Such units include vinylaromatics, methyl (meth)acrylate, phenyl(meth)acrylate, benzyl (meth)acrylate, methacrylamide or acrylonitrile.
  • any amount of binder can be used.
  • the amount of the binder is advantageously from 40 to 99.8% by weight, preferably from 70 to 99.4% by weight, particularly preferably from 80 to 99% by weight, based in each case on the total weight of the nonvolatile components of the coating.
  • the polycondensate is a phenolic resin, such as a novolac, a resole or a polyvinylphenol.
  • the novolac is preferably a cresol/formaldehyde or a cresol/xylenol/formaldehyde novolac, the amount of novolac advantageously being at least 50% by weight, preferably at least 80% by weight, based in each case on the total weight of all binders.
  • the dissolution behavior of the oleophilic layer in the developer can be fine-tuned by optional solubility regulating components. More particularly, development accelerators and development inhibitors can be used. These ingredients can be added to the oleophilic layer and/or to (an)other layer(s) of the coating.
  • Development accelerators are compounds which act as dissolution promoters because they are capable of increasing the dissolution rate of the oleophilic layer.
  • cyclic acid anhydrides, phenols or organic acids can be used in order to improve the aqueous developability.
  • the cyclic acid anhydride include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,6-endoxy-4-tetrahydro-phthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride, alpha -phenylmaleic anhydride, succinic anhydride, and pyromellitic anhydride, as described in U.S.
  • Patent No. 4,115,128 examples include bisphenol A, p-nitrophenol, p-ethoxyphenol, 2,4,4'-trihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 4-hydroxybenzophenone, 4,4',4"-trihydroxytriphenylmethane, and 4,4',3",4"-tetrahydroxy-3,5,3',5'-tetramethyltriphenyl-methane, and the like.
  • Examples of the organic acids include sulfonic acids, sulfinic acids, alkylsulfuric acids, phosphonic acids, phosphates, and carboxylic acids, as described in, for example, JP-A Nos. 60-88,942 and 2-96,755.
  • organic acids include p-toluenesulfonic acid, dodecylbenzenesulfonic acid, p-toluenesulfinic acid, ethylsulfuric acid, phenylphosphonic acid, phenylphosphinic acid, phenyl phosphate, diphenyl phosphate, benzoic acid, isophthalic acid, adipic acid, p-toluic acid, 3,4-dimethoxybenzoic acid, 3,4,5-trimethoxybenzoic acid, 2,3,4-trimethoxycinnamic acid, phthalic acid, terephthalic acid, 4-cyclohexene-1,2-dicarboxylic acid, erucic acid, lauric acid, n-undecanoic acid, and ascorbic acid.
  • the amount of the cyclic acid anhydride, phenol, or organic acid contained in the coating is preferably in the range of 0.05 to 20% by weight.
  • the coating also contains developer resistance means, also called development inhibitors, i.e. one or more ingredients which are capable of delaying the dissolution of the unexposed areas during processing.
  • developer resistance means also called development inhibitors, i.e. one or more ingredients which are capable of delaying the dissolution of the unexposed areas during processing.
  • the dissolution inhibiting effect is preferably reduced by heating, so that the dissolution of the exposed areas is not delayed and a large dissolution differential between exposed and unexposed areas can thereby be obtained.
  • developer resistance means can be added to the oleophilic layer or to another layer of the material.
  • Inhibitors of this type typically comprise a hydrogen bridge forming group such as nitrogen atoms, onium groups, carbonyl (-CO-), sulfinyl (-SO-) or sulfonyl (-SO 2 -) groups and a large hydrophobic moiety such as one or more aromatic nuclei.
  • the barrier layer preferably comprises a polymeric material which is insoluble in or impenetrable by the developer, e.g.
  • the solubility of the barrier layer in the developer or the penetrability of the barrier layer by the developer can be reduced by exposure to heat or infrared light.
  • inhibitors of the latter type include water-repellent polymers such as a polymer comprising siloxane and/or perfluoroalkyl units.
  • the precursor comprises a barrier layer which contains such a water-repellent polymer in a suitable amount between 0.5 and 25 mg/m 2 , preferably between 0.5 and 15 mg/m 2 and most preferably between 0.5 and 10 mg/m 2 . Higher or lower amounts are also suitable, depending on the hydrophobic/oleophobic character of the compound.
  • the water-repellent polymer is also ink-repelling, e.g.
  • the polysiloxane may be a linear, cyclic or complex cross-linked polymer or copolymer.
  • the term polysiloxane compound shall include any compound which contains more than one siloxane group -Si(R,R')-O-, wherein R and R' are optionally substituted alkyl or aryl groups.
  • Preferred siloxanes are phenylalkylsiloxanes and dialkylsiloxanes.
  • the number of siloxane groups in the (co)polymer is at least 2, preferably at least 10, more preferably at least 20. It may be less than 100, preferably less than 60.
  • the water-repellant polymer is a block-copolymer or a graft-copolymer of a poly(alkylene oxide) and a polymer comprising siloxane and/or perfluoroalkyl units.
  • a suitable copolymer comprises about 15 to 25 siloxane units and 50 to 70 alkyleneoxide groups.
  • Preferred examples include copolymers comprising phenylmethylsiloxane and/or dimethylsiloxane as well as ethylene oxide and/or propylene oxide, such as Tego Glide 410, Tego Wet 265, Tego Protect 5001 or Silikophen P50/X, all commercially available from Tego Chemie, Essen, Germany.
  • Such a copolymer acts as a surfactant which upon coating, due to its bifunctional structure, tends to position itself at the interface between the coating and air and thereby forms a separate top layer even when applied as an ingredient of the coating solution of the oleophilic layer. Simultaneously, such surfactants act as a spreading agent which improves the coating quality.
  • the water-repellent polymer can be applied in a second solution, coated on top of the oleophilic layer.
  • a solvent in the second coating solution that is not capable of dissolving the ingredients present in the first layer so that a highly concentrated water-repellent phase is obtained at the top of the material.
  • the protective layer generally comprises at least one water-soluble polymeric binder, such as polyvinyl alcohol, polyvinylpyrrolidone, partially hydrolyzed polyvinyl acetates, gelatin, carbohydrates or hydroxyethylcellulose, and can be produced in any known manner such as from an aqueous solution or dispersion which may, if required, contain small amounts, i.e. less than 5% by weight, based on the total weight of the coating solvents for the protective layer, of organic solvents.
  • the thickness of the protective layer can suitably be any amount, advantageously up to 5.0 ⁇ m, preferably from 0.1 to 3.0 ⁇ m, particularly preferably from 0.15 to 1.0 ⁇ m.
  • the coating and more specifically the oleophilic layer thereof may further contain additional ingredients.
  • additional ingredients are e.g. additional binders, especially sulfonamide and phthalimide groups containing polymers, to improve the run length and chemical resistance of the plate.
  • additional binders especially sulfonamide and phthalimide groups containing polymers
  • examples of such polymers are those described in EP-A 933682, EP-A 894622 and WO 99/63407.
  • colorants can be added such as dyes or pigments which provide a visible color to the coating and which remain in the coating at unexposed areas so that a visible image is produced after exposure and processing.
  • Typical examples of such contrast dyes are the amino-substituted tri- or diarylmethane dyes, e.g.
  • any known method can be used.
  • the above ingredients can be dissolved in a solvent mixture which does not react irreversibly with the ingredients and which is preferably tailored to the intended coating method, the layer thickness, the composition of the layer and the drying conditions.
  • Suitable solvents include ketones, such as methyl ethyl ketone (butanone), as well as chlorinated hydrocarbons, such as trichloroethylene or 1,1,1-trichloroethane, alcohols, such as methanol, ethanol or propanol, ethers, such as tetrahydrofuran, glycol-monoalkyl ethers, such as ethylene glycol monoalkyl ether, e.g.
  • 2-methoxy-1-propanol or propylene glycol monoalkyl ether and esters, such as butyl acetate or propylene glycol monoalkyl ether acetate. It is also possible to use a mixture which, for special purposes, may additionally contain solvents such as acetonitrile, dioxane, dimethylacetamide, dimethylsulfoxide or water.
  • Any coating method can be used for applying one or more coating solutions to the hydrophilic surface of the support.
  • a multi-layer coating can be applied by coating/drying each layer consecutively or by the simultaneous coating of several coating solutions at once.
  • the volatile solvents are removed from the coating until the coating is self-supporting and dry to the touch.
  • the residual solvent content may be regarded as an additional composition variable by means of which the composition may be optimized. Drying is typically carried out by blowing hot air onto the coating, typically at a temperature of at least 70°C, suitably 80-150°C and especially 90-140°C.
  • the drying time may typically be 15-600 seconds.
  • the material can be image-wise exposed directly with heat, e.g. by means of a thermal head, or indirectly by infrared light, preferably near infrared light.
  • the infrared light is preferably converted into heat by an IR light absorbing compound as discussed above.
  • the heat-sensitive lithographic printing plate precursor of the present invention is preferably not sensitive to visible light, i.e. no substantial effect on the dissolution rate of the coating in the developer is induced by exposure to visible light.
  • the coating is not sensitive to ambient daylight, i.e. visible (400-750 nm) and near UV light (300-400 nm) at an intensity and exposure time corresponding to normal working conditions so that the material can be handled without the need for a safe light environment.
  • the coating does not comprise photosensitive ingredients, such as (quinone)diazide or diazo(nium) compounds, photoacids, photoinitiators, sensitizers etc., which absorb the near UV and/or visible light that is present in sun light or office lighting and thereby change the solubility of the coating in exposed areas.
  • photosensitive ingredients such as (quinone)diazide or diazo(nium) compounds, photoacids, photoinitiators, sensitizers etc., which absorb the near UV and/or visible light that is present in sun light or office lighting and thereby change the solubility of the coating in exposed areas.
  • the printing plate precursor of the present invention can be exposed to infrared light by means of e.g. LEDs or a laser.
  • the light used for the exposure is a laser emitting near infrared light having a wavelength in the range from about 750 to about 1500 nm, such as a semiconductor laser diode, a Nd:YAG or a Nd:YLF laser.
  • the required laser power depends on the sensitivity of the image-recording layer, the pixel dwell time of the laser beam, which is determined by the spot diameter (typical value of modern plate-setters at 1/e 2 of maximum intensity : 10-25 ⁇ m), the scan speed and the resolution of the exposure apparatus (i.e. the number of addressable pixels per unit of linear distance, often expressed in dots per inch or dpi; typical value : 1000-4000 dpi).
  • ITD plate-setters for thermal plates are typically characterized by a very high scan speed up to 500 m/sec and may require a laser power of several Watts.
  • the known plate-setters can be used as an off-press exposure apparatus, which offers the benefit of reduced press down-time.
  • XTD plate-setter configurations can also be used for on-press exposure, offering the benefit of immediate registration in a multi-color press. More technical details of on-press exposure apparatuses are described in e.g. US 5,174,205 and US 5,163,368.
  • the non-image areas of the coating are removed by immersion in a conventional aqueous alkaline developer, which may be combined with mechanical rubbing, e.g. by a rotating brush.
  • a conventional aqueous alkaline developer which may be combined with mechanical rubbing, e.g. by a rotating brush.
  • any water-soluble protective layer present is also removed.
  • Silicate-based developers which have a ratio of silicon dioxide to alkali metal oxide of at least 1 are preferred to ensure that the alumina layer (if present) of the substrate is not damaged.
  • Preferred alkali metal oxides include Na 2 O and K 2 O, and mixtures thereof.
  • the developer may optionally contain further components, such as buffer substances, complexing agents, antifoams, organic solvents in small amounts, corrosion inhibitors, dyes, surfactants and/or hydrotropic agents as well known in the art.
  • the development is preferably carried out at temperatures of from 20 to 40 °C in automated processing units as customary in the art.
  • alkali metal silicate solutions having alkali metal contents of from 0.6 to 2.0 mol/l can suitably be used. These solutions may have the same silica/alkali metal oxide ratio as the developer (generally, however, it is lower) and likewise optionally contain further additives.
  • the required amounts of regenerated material must be tailored to the developing apparatuses used, daily plate throughputs, image areas, etc. and are in general from 1 to 50 ml per square meter of recording material.
  • the addition can be regulated, for example, by measuring the conductivity as described in EP-A 0 556 690.
  • the plate precursor according to the invention can, if required, then be post-treated with a suitable correcting agent or preservative as known in the art.
  • a suitable correcting agent or preservative as known in the art.
  • the layer can be briefly heated to elevated temperatures ("baking").
  • bakeout agents, correction agents and UV-curable printing inks also increases.
  • thermal post-treatment is described, inter alia, in DE-A 14 47 963 and GB-A 1 154 749.
  • the processing of the plate precursor may also comprise a rinsing step, a drying step and/or a gumming step.
  • the printing plate thus obtained can be used for conventional, so-called wet offset printing, in which ink and an aqueous dampening liquid is supplied to the plate.
  • Another suitable printing method uses so-called single-fluid ink without a dampening liquid.
  • Single-fluid inks which are suitable for use in the method of the present invention have been described in US 4,045,232; US 4,981,517 and US 6,140,392.
  • the single-fluid ink comprises an ink phase, also called the hydrophobic or oleophilic phase, and a polyol phase as described in WO 00/32705.
  • a 0.30 mm thick aluminum foil was degreased by immersing the foil in an aqueous solution containing 5 g/l of sodium hydroxide at 50°C and rinsed with demineralized water.
  • the foil was then electrochemically grained using an alternating current in an aqueous solution containing 4 g/l of hydrochloric acid, 4 g/l of hydroboric acid and 5 g/l of aluminum ions at a temperature of 35°C and a current density of 1200 A/m 2 to form a surface topography with an average center-line roughness Ra of 0.5 ⁇ m.
  • the aluminum foil was then etched with an aqueous solution containing 300 g/l of sulfuric acid at 60°C for 180 seconds and rinsed with demineralized water at 25°C for 30 seconds.
  • the foil was subsequently subjected to anodic oxidation in an aqueous solution containing 200 g/l of sulfuric acid at a temperature of 45°C, a voltage of about 10 V and a current density of 150 A/m 2 for about 300 seconds to form an anodic oxidation film of 3.00 g/m 2 of Al 2 O 3 then washed with demineralized water, post-treated with a solution containing polyvinylphosphonic acid and subsequently with a solution containing aluminum trichloride, rinsed with demineralized water at 20°C during 120 seconds and dried.
  • a layer of novolac (Alnovol SPN452 from Clariant, a 40.5 wt.% solution in methoxypropanol) and the dyes specified in Table 2 were coated on the above support. After drying during 1 min at 130°C, the samples contained 0.9 g/m 2 of novolac.
  • a series of unexposed samples is immersed in Agfa EP26 developer at 20°C, each sample during a different time period. After the immersion period, the sample was removed from the developer, immediately rinsed with water, dried and then the dissolution of the coating in the developer was measured by comparing the weight of the sample before and after the development. As soon as the coating is dissolved completely, no more weight loss is measured upon longer immersion time periods, i.e.
  • dissolution time a curve representing weight loss as a function of immersion time reaches a plateau from the moment of complete dissolution of the layer, which is referred to herein as "dissolution time".
  • Dye (mg/m 2 ) Dissolution time (sec) 1 (ref.) none 30 2 (inv.) IR-1 (35) 30 3 (inv.) IR-2 (35) 20 4 (inv.) IR-3 (35) 30 5 (inv.) IR-4 (35) 20 6 (inv.) IR-5 (35) 25 7 (comp.) C1 (35) 60
  • Examples 2-6 contained a dye according to the invention and showed equal or shorter dissolution time values than reference Example 1 without dye. Comparative Example 7 showed a longer dissolution time than the materials according to the invention.
  • the IR-sensitivity of the different compositions corresponds to the minimum energy density setting that is required to obtain a 50% reduction of the light absorption of the coating, measured on the developed plate at the wavelength maximum of the contrast dye, in areas which have been exposed with a dot area of a 50% screen (@200 lpi).

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Thermal Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials For Photolithography (AREA)
  • Printing Plates And Materials Therefor (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
EP20020102303 2002-09-04 2002-09-04 Wärmeempfindlicher Flachdruckplattenvorläufer Expired - Lifetime EP1396338B1 (de)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP20020102303 EP1396338B1 (de) 2002-09-04 2002-09-04 Wärmeempfindlicher Flachdruckplattenvorläufer
DE2002613236 DE60213236T2 (de) 2002-09-04 2002-09-04 Wärmeempfindlicher Flachdruckplattenvorläufer
JP2003310344A JP2004102279A (ja) 2002-09-04 2003-09-02 感熱性平版印刷版前駆体
US10/654,508 US20040048195A1 (en) 2002-09-04 2003-09-03 Heat-sensitive lithographic printing plate precursor

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1759836A2 (de) 2005-08-29 2007-03-07 Fuji Photo Film Co., Ltd. Lithographischer Druckplattenvorläufer, lithographische Druckmethode und Cyanin Farbstoff
EP3130465A1 (de) * 2015-08-12 2017-02-15 Agfa Graphics Nv Wärmeempfindlicher lithografiedruckplattenvorläufer

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Publication number Priority date Publication date Assignee Title
GB1084070A (en) 1960-08-05 1967-09-20 Kalle Ag Process and material for the preparation of planographic printing plates
EP0537633A1 (de) 1991-10-16 1993-04-21 Hoechst Aktiengesellschaft Verfahren zur Behandlung von aufgerauhten und anodisierten Flachdruckplatten und danach hergestellte Flachdruckplatten
EP0659909A1 (de) 1993-12-22 1995-06-28 Hoechst Aktiengesellschaft Verfahren zur elektrochemischen Aufrauhung
DE4417907A1 (de) 1994-05-21 1995-11-23 Hoechst Ag Verfahren zur Nachbehandlung von platten-, folien- oder bandförmigem Material, Träger aus derartigem Material und seine Verwendung für Offsetdruckplatten
DE4423140A1 (de) 1994-07-01 1996-01-04 Hoechst Ag Hydrophiliertes Trägermaterial und damit hergestelltes Aufzeichnungsmaterial
WO1997039894A1 (en) 1996-04-23 1997-10-30 Horsell Graphic Industries Limited Heat-sensitive composition and method of making a lithographic printing form with it
EP0823327A2 (de) 1996-08-06 1998-02-11 Mitsubishi Chemical Corporation Positiv arbeitendes strahlungsempfindliches Gemisch, positiv arbeitende lichtempfindliche Flachdruckplatte und Verfahren zur Herstellung einer positiv arbeitenden lithographischen Druckplatte
EP0978376A2 (de) 1998-08-01 2000-02-09 Agfa-Gevaert AG Strahlungsempfindlisches Gemisch mit IR-absorbierenden, betainischen oder betainisch-anionischen Cyaninfarbstoffen und damit hergestelltes Aufzeichnungsmaterial
EP1147885A2 (de) * 2000-04-20 2001-10-24 Fuji Photo Film Co., Ltd. Lithographische Druckplattenvorläufer
EP1223196A2 (de) * 2001-01-15 2002-07-17 Fuji Photo Film Co., Ltd. Negativfilm-Aufzeichnungsmaterial und Cyaninfarbstoff

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1084070A (en) 1960-08-05 1967-09-20 Kalle Ag Process and material for the preparation of planographic printing plates
EP0537633A1 (de) 1991-10-16 1993-04-21 Hoechst Aktiengesellschaft Verfahren zur Behandlung von aufgerauhten und anodisierten Flachdruckplatten und danach hergestellte Flachdruckplatten
EP0659909A1 (de) 1993-12-22 1995-06-28 Hoechst Aktiengesellschaft Verfahren zur elektrochemischen Aufrauhung
DE4417907A1 (de) 1994-05-21 1995-11-23 Hoechst Ag Verfahren zur Nachbehandlung von platten-, folien- oder bandförmigem Material, Träger aus derartigem Material und seine Verwendung für Offsetdruckplatten
DE4423140A1 (de) 1994-07-01 1996-01-04 Hoechst Ag Hydrophiliertes Trägermaterial und damit hergestelltes Aufzeichnungsmaterial
WO1997039894A1 (en) 1996-04-23 1997-10-30 Horsell Graphic Industries Limited Heat-sensitive composition and method of making a lithographic printing form with it
EP0823327A2 (de) 1996-08-06 1998-02-11 Mitsubishi Chemical Corporation Positiv arbeitendes strahlungsempfindliches Gemisch, positiv arbeitende lichtempfindliche Flachdruckplatte und Verfahren zur Herstellung einer positiv arbeitenden lithographischen Druckplatte
EP0978376A2 (de) 1998-08-01 2000-02-09 Agfa-Gevaert AG Strahlungsempfindlisches Gemisch mit IR-absorbierenden, betainischen oder betainisch-anionischen Cyaninfarbstoffen und damit hergestelltes Aufzeichnungsmaterial
US20020006575A1 (en) * 1998-08-01 2002-01-17 Otfried Gaschler Radiation-sensitive mixtures comprising ir-absorbing cyanine dyes having a betaine structure or having a betaine structure and containing an anion, and recording materials prepared therewith
EP1147885A2 (de) * 2000-04-20 2001-10-24 Fuji Photo Film Co., Ltd. Lithographische Druckplattenvorläufer
EP1223196A2 (de) * 2001-01-15 2002-07-17 Fuji Photo Film Co., Ltd. Negativfilm-Aufzeichnungsmaterial und Cyaninfarbstoff

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1759836A2 (de) 2005-08-29 2007-03-07 Fuji Photo Film Co., Ltd. Lithographischer Druckplattenvorläufer, lithographische Druckmethode und Cyanin Farbstoff
EP1759836A3 (de) * 2005-08-29 2008-01-23 FUJIFILM Corporation Lithographischer Druckplattenvorläufer, lithographische Druckmethode und Cyanin Farbstoff
CN1924703B (zh) * 2005-08-29 2012-05-30 富士胶片株式会社 平版印刷版前体、平版印刷方法和新型花青染料
EP3130465A1 (de) * 2015-08-12 2017-02-15 Agfa Graphics Nv Wärmeempfindlicher lithografiedruckplattenvorläufer
WO2017025307A1 (en) * 2015-08-12 2017-02-16 Agfa Graphics Nv Heat-sensitive lithographic printing plate precursor
CN107921775A (zh) * 2015-08-12 2018-04-17 爱克发有限公司 热敏平版印版原版

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DE60213236D1 (de) 2006-08-31
JP2004102279A (ja) 2004-04-02
EP1396338B1 (de) 2006-07-19

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