EP0908307B1 - Verfahren zur Herstellung einer positiv arbeitenden Druckplatte aus einem Wärmeempfindlichen Bildaufzeichnungsmaterial - Google Patents

Verfahren zur Herstellung einer positiv arbeitenden Druckplatte aus einem Wärmeempfindlichen Bildaufzeichnungsmaterial Download PDF

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Publication number
EP0908307B1
EP0908307B1 EP19980203122 EP98203122A EP0908307B1 EP 0908307 B1 EP0908307 B1 EP 0908307B1 EP 19980203122 EP19980203122 EP 19980203122 EP 98203122 A EP98203122 A EP 98203122A EP 0908307 B1 EP0908307 B1 EP 0908307B1
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EP
European Patent Office
Prior art keywords
layer
printing plates
dyes
lithographic printing
imaging element
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EP19980203122
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English (en)
French (fr)
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EP0908307A3 (de
EP0908307A2 (de
Inventor
Marc Van Damme
Joan Vermeersch
Geert Deroover
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Agfa Gevaert NV
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Agfa Gevaert NV
Agfa Gevaert AG
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Priority to EP19980203122 priority Critical patent/EP0908307B1/de
Publication of EP0908307A2 publication Critical patent/EP0908307A2/de
Publication of EP0908307A3 publication Critical patent/EP0908307A3/de
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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
    • 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
    • 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
    • B41C2210/14—Multiple imaging layers
    • 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

Definitions

  • the present invention relates to a method for preparing a lithographic printing plate using a heat mode imaging element comprising an IR sensitive top layer. More specifically the invention is related to a method for preparing a lithographic printing plate using a heat mode imaging element whereby the capacity of the top layer of being penetrated and/or solubilised by an aqueous developer is changed upon exposure.
  • Lithography is the process of printing from specially prepared surfaces, some areas of which are capable of accepting lithographic ink, whereas other areas, when moistened with water, will not accept the ink.
  • the areas which accept ink form the printing image areas and the ink-rejecting areas form the background areas.
  • a photographic material is made imagewise receptive to oily or greasy inks in the photo-exposed (negative-working) or in the non-exposed areas (positive-working) on a hydrophilic background.
  • lithographic printing plates also called surface litho plates or planographic printing plates
  • a support that has affinity to water or obtains such affinity by chemical treatment is coated with a thin layer of a photosensitive composition.
  • Coatings for that purpose include light-sensitive polymer layers containing diazo compounds, dichromate-sensitized hydrophilic colloids and a large variety of synthetic photopolymers. Particularly diazo-sensitized systems are widely used.
  • the exposed image areas become insoluble and the unexposed areas remain soluble.
  • the plate is then developed with a suitable liquid to remove the diazonium salt or diazo resin in the unexposed areas.
  • printing plates are known that include a photosensitive coating that upon image-wise exposure is rendered soluble at the exposed areas. Subsequent development then removes the exposed areas.
  • a typical example of such photosensitive coating is a quinone-diazide based coating.
  • the above described photographic materials from which the printing plates are made are camera-exposed through a photographic film that contains the image that is to be reproduced in a lithographic printing process.
  • Such method of working is cumbersome and labor intensive.
  • the printing plates thus obtained are of superior lithographic quality.
  • GB-1 492 070 discloses a method wherein a metal layer or a layer containing carbon black is provided on a photosensitive coating. This metal layer is then ablated by means of a laser so that an image mask on the photosensitive layer is obtained. The photosensitive layer is then overall exposed by UV-light through the image mask. After removal of the image mask, the photosensitive layer is developed to obtain a printing plate.
  • This method however still has the disadvantage that the image mask has to be removed prior to development of the photosensitive layer by a cumbersome processing.
  • thermoplastic polymer particles By image-wise exposure to an infrared laser, the thermoplastic polymer particles are image-wise coagulated thereby rendering the surface of the imaging element at these areas ink-acceptant without any further development.
  • a disadvantage of this method is that the printing plate obtained is easily damaged since the non-printing areas may become ink accepting when some pressure is applied thereto. Moreover, under critical conditions, the lithographic performance of such a printing plate may be poor and accordingly such printing plate has little lithographic printing latitude.
  • US-P- 4 708 925 discloses imaging elements including a photosensitive composition comprising an alkali-soluble novolac resin and an onium-salt. This composition can optionally contain an IR-sensitizer. After image-wise exposing said imaging element to UV - visible - or IR-radiation followed by a development step with an aqueous alkali liquid there is obtained a positive or negative working printing plate. The printing results of a lithographic plate obtained by irradiating and developing said imaging element are poor.
  • EP-A- 625 728 discloses an imaging element comprising a layer which is sensitive to UV- and IR-irradiation and which can be positive or negative working.
  • This layer comprises a resole resin, a novolac resin, a latent Bronsted acid and an IR-absorbing substance.
  • the printing results of a lithographic plate obtained by irradiating and developing said imaging element are poor.
  • US-P- 5 340 699 is almost identical with EP-A- 625 728 but discloses the method for obtaining a negative working IR-laser recording imaging element.
  • the IR-sensitive layer comprises a resole resin, a novolac resin, a latent Bronsted acid and an IR-absorbing substance.
  • the printing results of a lithographic plate obtained by irradiating and developing said imaging element are poor.
  • EP-A- 678 380 discloses a method wherein a protective layer is provided on a grained metal support underlying a laser-ablatable surface layer. Upon image-wise exposure the surface layer is fully ablated as well as some parts of the protective layer. The printing plate is then treated with a cleaning solution to remove the residu of the protective layer and thereby exposing the hydrophilic surface layer.
  • GB-A-1 245 924 discloses an information recording method wherein a recording material is used comprising a heat-sensitive recording layer of a composition such that the solubility of any given area of the layer in a given solvent can be increased by heating that area of the layer, wherein the said layer is information-wise heated to produce a record of the information in terms of a difference in the solubilities in the said solvent of different areas of the recording layer, and wherein the whole layer is then contacted with such solvent to cause the portions of the recording layer which are soluble or most soluble in such solvent to be removed or penetrated by such solvent.
  • EP-A-347 245 discloses a method for development-processing of presensitized plates for use in making lithographic printing plates which comprises imagewise exposing the presensitized plate to light and development-processing the exposed presensitized plate with an alkaline developer and a replenisher, wherein the developerand the replenisher are aqueous solutions of an alkali metal silicate and the ratio (SiO 2 ):(M 2 O) (wherein (SiO 2 ) and (M 2 O) are the molar concentrations of respectively SiO 2 and an alkali metal oxide M 2 O) of the replenisher ranges from 0.6 to 1.5.
  • EP-A- 732 628 discloses an aqueous alkaline developing solution comprising an alkaline composition of at least one compound selected from the group consisting of alkali metal silicate and alkali metal metasilicate, wherein the M 2 O/SiO 2 molar ratio of said alkaline mixture is in the range from 0.5 to 1.2, the total content of said alkaline mixture being in the range of from 5 to 15 % by weight of total developing solution, and wherein said developing solution comprises a non-ionic surfactant and at least another surfactant selected from the group consisting of anionic surfactants and amphoteric surfactants.
  • US-P- 5 466 557 discloses a radiation-sensitive composition
  • a radiation-sensitive composition comprising (1) a resole resin, (2) a novolac resin, (3) a latent Bronsted acid, (4) an infrared absorber, and (5) terephthalaldehyde.
  • GB-A- 1 155 035 discloses a method of recording information, wherein a recording material is used comprising a layer of a polymeric material which when any given area of the layer is sufficiently heated undergoes in that area a modification resulting in a decrease in the solubility of that area of the layer in water or an aqueous medium, such layer also incorporating a substance or substances distributed over the whole area of the layer and being capable of being heated by exposing the layer to intense radiant energy which is absorbed by such substance or substances, and wherein the said material is exposed to intense radiant energy which is distributed over the material in a pattern determined by the information to be recorded and which is at least partly absorbed by said distributed substance or substances, so that a corresponding heat pattern is generated in the material, whereby such information is recorded in terms of a difference in the solubilities in water or an aqueous medium of different areas of said layer.
  • GB-A- 1 154 568 discloses a method of recording a graphic original having contrasting light-absorbing and light-transmitting areas, wherein a recording material comprising a supported layer composed mainly of gelatin the water-solubility or water-absorptive capacity of which increases if the layer is sufficiently heated , such layer also having light absorbing substance(s) distributed therein, is placed with such gelatin layer in contact with the light-absorbing areas of the original and the said gelatin layer is exposed to light through the original, the intensity of the light and the duration of the exposure being such that the areas of the gelatin layer in contact with the light-absorbing areas of the original are substantially unaffected by heat conduction from such light-absorbing areas, but the water-solubility or water-absorptive capacity of the other areas of the gelatin layer is increased by heating thereof due to absorption of copying light by the light-absorbing substance(s) in those other areas of the gelatin layer.
  • a method for making lithographic printing plates including the following steps
  • a method according to the invention for making lithographic printing plates including the following steps
  • the top layer in accordance with the present invention consists of an IR-dye and preferably of an IR-dye and a binder resin.
  • a mixture of IR-dyes may be used, but it is preferred to use only one IR-dye.
  • Suitable IR-dyes are known since a long time and belong to several different chemical classes, e.g.
  • indoaniline dyes especially for irradiation with a laser source with an emission spectrum of about 1060 nm belongs to the scope of the general formula of the German patent application DE- 4. 31 162 .
  • This general formula (I) is represented by : wherein K represents Q together with a counterion An-, or wherein Q represents chlorine, fluorine, bromine, iodine, alkyloxy, aryloxy, dialkylamino, diarylamino, alkylarylamino, nitro, cyano, alkylsulphonyl, arylsulphonyl, heterocyclyl, or a moiety represented by L-S-, wherein L represents alkyl, aryl, heterocyclyl, cyano or substituted carbonyl, thiocarbonyl or iminocarbonyl, An- represents an anion commonly used in the chemistry of cationic dyes, or an equivalent thereof, B 1 represents cyano, alkoxycarbonyl, alkyl- or arylcarbonyl, or aminocarbonyl optionally substituted once or twice at the nitrogen atom by alkyl and/or aryl, B 2 represents arylsulphonyl, alkylsulphon
  • R1, R2, R17 and R18 have the same meaning as R3, and B1, B2, the other R symbols, T, and the D symbols are defined as hereinbefore, and ⁇ is 0 or 1.
  • infra-red absorbing dyes corresponding to general formula (I) or to one of the preferred subclasses defined above which are chosen for the determination of specific spectral characteristics are listed below. A reference number is designated to them by which they will be identified in the tables furtheron of the description and examples :
  • IRD-14 is a commercial product known as CYASORB IR165, marketed by American Cyanamid Co, Glendale Protective Technologie Division, Woodbury, New-York. It is a mixture of two parts of the molecular non-ionic form (IRD-14a) and three parts of the ionic form (IRD-14b) represented by :
  • IR-dyes especially for irradiation with a laser source with an emission spectrum of about 830 nm belong to the scope of the following general formulas.
  • R 72 may also represents halogen, NR 88 R 89 (R 88 ,R 89 each independently represents alkyl, aryl, or may form a (hetero)cyclic ring), PR 88 R 89 , ester-COOR 92 (R 92 represents alkyl, or aryl), barbituric acid group (with optionally substituted N-atoms).
  • R 71 or R 73 may represents : -OCOR 93 ; R 93 represents alkyl, or aryl.
  • R 77 together with R 78 , R 78 together with R 79 , R 79 together with R 80 , R 81 together with R 82 , R 82 together with R 83 , R 83 together with R 84 may form an annulated benzoring optionally substituted with a carbocyclic acid, ester or sulphogroup.
  • R 78 , R 79 , R 82 , R 83 each independently may represent hydrogen, alkyl, aryl, halogen, ester, carbocyclic acid, amide, amine, nitrile, alkoxy, aryloxy, or sulpho group.
  • R 85 , R 86 , R 87 , R 88 each independently may represent an alkylgroup, R 85 together with R 86 , R 87 together with R 88 may form a cyclic (spiro)ring.
  • R 75 , R 76 each independently represents an alkyl, aryl group;-C n H 2n SO 3 M (n represents an integer from 2 to 4 and M H or positively charged counterion); - C n H 2n COOM (n represents an integer from 1 to 5 and M H or positively charged counterion); -C n H 2n COOR 94 (n represents an integer from 1 to 5 and R 94 alkyl, or aryl group);-L1-CONHSO 2 R 95 (L1 represents -C n H 2n - with n an integer from 1 to 4 and R 95 alkyl or aryl).
  • R 96 , R 102 represents alkyl, or aryl group; - C n H 2n SO 3 M (n represents an integer from 2 to 4 and M H or positively charged counterion);;-C n H 2n COOM (n represents an integer from 1 to 5 and M H or positively charged counterion); -C n H 2n COOR 103 (n represents an integer from 1 to 5 and R 103 alkyl, or aryl group); -L1-CONHSO 2 R 104 (L1 represents - C n H 2n - with n an integer from 1 to 4 and R 104 alkyl or aryl).
  • R 97 , R 98 R 100 , R 101 may each independently represent : hydrogen, alkyl, aryl; R 97 together with R 98 , R 100 together with R 101 may form an annulated benzoring.
  • R 98 may represent : hydrogen, alkyl, aryl, halogen, ester, or-SO2R 105 (R 105 represents an alkyl or aryl).
  • R 106 , R 107 , R 108 , R 109 each independently may represent alkyl, aryl group;- C n H 2n SO 3 M represents an integer from 2 to 4 and M H or positively charged counterion); -C n H 2n COOM (n represents an integer from 1 to 5 and M H or positively charged counterion); -C n H 2n COOR 117 (n represents an integer from 1 to 5 and R 117 alkyl, or aryl group); - L1-CONHSO 2 R 118 (L1 represents -C n H 2n - with n an integer from 1 to 4 and R 118 alkyl or aryl).
  • R 110 , R 111 , R 112 , R 113 each independently represents : hydrogen, alkyl, or aryl group.
  • R 114 , R 115 , R 116 each indepentdently may represent : hydrogen, alkyl, or aryl group;
  • R 115 represents halogen, ester, or-SO2R 119 (R 119 represents alkyl, or aryl).
  • R 120 , R 121 , R 122 , R 123 R 124 , R 125 , R 126 , R 127 each independently may represent alkyl, aryl group; - C n H 2n SO 3 M (n represents an integer from 2 to 4 and M H or positively charged counterion);;-C n H 2n COOM (n represents an integer from 1 to 5 and M H or positively charged counterion); -C n H 2n COOR 131 (n represents an integer from 1 to 5 and R 131 alkyl, or aryl group); -L1-CONHSO 2 R 132 (L1 represents -C n H 2n - with n an integer from 1 to 4 and R 132 alkyl or aryl).
  • R 120 together with R 121 , R 122 together with R 123 , R 124 together with R 125 , R 126 together with R 127 may form a cyclic ring.
  • R 128 , R 129 , R 130 each independently may represents hydrogen, alkyl, or aryl group; R 129 may represent : halogen, ester, or -SO2R 133 (R 133 represents alkyl, or aryl).
  • R 134 , R 137 , R 138 , R 141 each independently may represent : hydrogen, alkyl, or aryl R 134 together with R 135 , R 141 together with R 140 may form a carbocyclic ring.
  • R 135 together with R 136 , R 139 together with R 140 may form a carbocyclic ring.
  • R 135 , R 136 , R 139 , R 140 each independently may represent: hydrogen, alkyl, aryl group; - C n H 2n SO 3 M (n represents an integer from 2 to 4 and M H or positively charged counterion);; - C n H 2n COOM (n represents an integer from 1 to 5 and M H or positively charged counterion);
  • R 142 , R 143 , R 144 , R 145 each independently represents alkyl, aryl group; - C n H 2n SO 3 M represents an integer from 2 to 4 and M H or positively charged counterion);; -C n H 2n COOM (n represents an integer from 1 to 5 and M H or positively charged counterion); -C n H 2n COOR 146 (n represents an integer from 1 to 5 and R 146 alkyl, or aryl group); - L1-CON
  • binder resin in the top layer gelatin cellulose, cellulose esters e.g. cellulose acetate, polyvinyl alcohol, polyvinyl pyrrolidone, a copolymer of vinylidene chloride and acrylonitrile, poly(meth)acrylates, polyvinyl chloride, nitrocellulose, silicone resins etc.
  • binder resin are hydrophobic binder resins, more preferably phenolic resins e.g. novolacs and vinyl phenols.
  • the IR-dyes are present preferably in an amount between 10 and 80 parts by weight of the total amount of said IR-sensitive top layer.
  • the total amount of the top layer preferably ranges from 0.1 to 10 g/m2 more preferably from 0.3 to 2 g/m2.
  • top layer a difference in the capacity of being penetrated and/or solubilised by the aqueous alkaline solution is generated upon image-wise exposure according to the invention.
  • the said capacity is increased upon image-wise IR exposure to such degree that the imaged parts of the top layer and the underlying areas of the first layer will be cleaned out during development without solubilising and/or damaging the non-imaged parts.
  • the development with the aqueous alkaline solution is preferably done within an interval of 5 to 120 seconds.
  • the present invention comprises a first layer soluble in an aqueous developing solution, more preferably an aqueous alkaline developing solution with a pH between 7.5 and 14. Said layer is preferably contiguous to the top layer.
  • the alkali soluble polymers used in this layer are preferably hydrophobic and ink accepting polymers as used in conventional positive or negative working PS-plates e.g. novolac, polyvinyl phenols, carboxy substituted polymers etc. Typical examples of these polymers are descibed in DE-A- 4 007 428, DE-A- 4 027 301 and DE-A- 4 445 820.
  • the hydrophobic polymer used in connection with the present invention is further characterised by insolubility in water and at least partial solubility/swellability in an alkaline solution and/or at least partial solubility in water when combined with a cosolvent.
  • this aqueous alkali soluble layer is preferably a visible light- and UV-light desensitised layer.
  • Said layer is preferably thermally hardenable.
  • This preferably visible light- or UV-light desensitised layer does not comprise photosensitive ingredients such as diazo compounds, photoacids, photoinitiators, quinone diazides, sensitisers etc. which absorb in the wavelength range of 250nm to 650nm. In this way a daylight stable printing plate can be obtained.
  • Said first layer preferably also includes a low molecular acid, preferably a carboxylic acid, still more preferably a benzoic acid, most preferably 3,4,5-trimethoxybenzoic acid.
  • the ratio between the total amount of low molecular acid and polymer in the first layer preferably ranges from 2:98 to 40:60, more preferably from 5:95 to 20:80.
  • the total amount of said first layer preferably ranges from 0.1 to 10 g/m 2 , more preferably from 0.3 to 2 g/m 2 .
  • the lithographic base can be an anodised aluminum.
  • a particularly preferred lithographic base is an electrochemically grained and anodised aluminum support.
  • the anodised aluminum support may be treated to improve the hydrophilic properties of its surface.
  • the aluminum support may be silicated by treating its surface with 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 can 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, polyvinylsulphonic acid, polyvinylbenzenesulphonic acid, sulphuric acid esters of polyvinyl alcohol, and acetals of polyvinyl alcohols formed by reaction with a sulphonated aliphatic aldehyde It is further evident that one or more of these post treatments may be carried out alone or in combination.
  • the lithographic base having a hydrophilic surface comprises a flexible support, such as e.g. paper or plastic film, provided with a cross-linked hydrophilic layer.
  • a particularly suitable cross-linked hydrophilic layer may be obtained from a hydrophilic binder cross-linked with a cross-linking agent such as formaldehyde, glyoxal, polyisocyanate or a hydrolysed tetra-alkylorthosilicate. The latter is particularly preferred.
  • hydrophilic binder there may be used hydrophilic (co)polymers such as for example, homopolymers and copolymers of vinyl alcohol, acrylamide, methylol acrylamide, methylol methacrylamide, acrylic acid, methacrylic 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 percent by weight, preferably 80 percent by weight.
  • the amount of crosslinking agent, in particular of tetraalkyl orthosilicate, is preferably at least 0.2 parts by weight per part by weight of hydrophilic binder, more preferably between 0.5 and 5 parts by weight, most preferably between 1.0 parts by weight and 3 parts by weight.
  • a cross-linked hydrophilic layer in a lithographic base used in accordance with the present embodiment preferably also contains 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 can be added e.g. silica prepared according to Stöber as described in J. Colloid and Interface Sci., Vol.
  • 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 thickness of a cross-linked hydrophilic layer in a lithographic base in accordance with this embodiment may vary in the range of 0.2 to 25 ⁇ m and is preferably 1 to 10 ⁇ m.
  • plastic film e.g. substrated polyethylene terephthalate film, cellulose acetate film, polystyrene film, polycarbonate film etc.
  • the plastic film support may be opaque or transparent.
  • the amount of silica in the adhesion improving layer is between 200 mg per m 2 and 750 mg per m 2 .
  • the ratio of silica to hydrophilic binder is preferably more than 1 and the surface area of the colloidal silica is preferably at least 300 m 2 per gram, more preferably at least 500 m 2 per gram.
  • Image-wise exposure in connection with the present invention is an image-wise scanning exposure involving the use of a laser that operates in the infrared or near-infrared, i.e. wavelength range of 700-1500 nm. Most preferred are laser diodes emitting in the near-infrared. Exposure of the imaging element can be performed with lasers with a short as well as with lasers with a long pixel dwell time. Preferred are lasers with a pixel dwell time between 0.005 ⁇ s and 20 ⁇ s.
  • the heat mode imaging element is developed by rinsing it with an aqueous alkaline solution.
  • aqueous alkaline solutions used in the present invention are those that are used for developing conventional positive working presensitised printing plates and have preferably a pH between 11.5 and 14.
  • the imaged parts of the top layer that were rendered more penetrable for the aqueous alkaline solution upon exposure and the corresponding parts of the underlying layer are cleaned-out whereby a positive working printing plate is obtained.
  • the composition of the developer used is also very important.
  • the developers and replenishers for developer used in the invention are preferably aqueous solutions mainly composed of alkali metal silicates and alkali metal hydroxides represented by MOH or their oxyde, represented by M 2 O., wherein said developer contains SiO 2 and M 2 O in a molar ratio of 0.5 to 1.5 and a concentration of SiO 2 of 0.5 to 5% by weight.
  • alkali metal silicates preferably used are, for instance, sodium silicate, potassium silicate, lithium silicate and sodium metasilicate.
  • alkali metal hydroxides preferred are sodium hydroxide, potassium hydroxide and lithium hydroxide.
  • the developers used in the invention may simultaneously contain other alkaline agents.
  • other alkaline agents include such inorganic alkaline agents as ammonium hydroxide, sodium tertiary phosphate, sodium secondary phosphate, potassium tertiary phosphate, potassium secondary phosphate, ammonium tertiary phosphate, ammonium secondary phosphate, sodium bicarbonate, sodium carbonate, potassium carbonate and ammonium carbonate; and such organic alkaline agents as mono-, di- or triethanolamine, mono-, di-or trimethylamine, mono-, di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-, di- or triisopropanolamine, ethyleneimine, ethylenediimine and tetramethylammonium hydroxide.
  • the concentration of SiO 2 in the developer and replenisher preferably ranges from 1 to 4 % by weight. Such limitation of the concentration of SiO 2 makes it possible to stably provide lithographic printing plates having good finishing qualities even when a large amount of plates according to the invention are processed for a long time period.
  • an aqueous solution of an alkali metal silicate having a molar ratio [SiO 2 ] / [M 2 O], which ranges from 1.0 to 1.5 and a concentration of SiO 2 of 1 to 4 % by weight is used as a developer.
  • a replenisher having alkali strength equal to or more than that of the developer is employed.
  • a molar ratio, [SiO 2 ] / [M 2 O] of the replenisher is equal to or smaller than that of the developer, or that a concentration of SiO 2 is high if the molar ratio of the developer is equal to that of the replenisher.
  • organic solvents having solubility in water at 20 °C of not more than 10 % by weight according to need.
  • organic solvents are such carboxilic acid esters as ethyl acetate, propyl acetate, butyl acetate, amyl acetate, benzyl acetate, ethylene glycol monobutyl acetate, butyl lactate and butyl levulinate; such ketones as ethyl butyl ketone, methyl isobutyl ketone and cyclohexanone; such alcohols as ethylene glycol monobutyl ether, ethylene glycol benzyl ether, ethylene glycol monophenyl ether, benzyl alcohol, methylphenylcarbinol, n-amyl alcohol and methylamyl alcohol; such alkyl-substituted aromatic hydrocarbons as xylene; and such halogenated hydrocarbons
  • organic solvents may be used alone or in combination. Particularly preferred is benzyl alcohol in the invention. These organic solvents are added to the developer or replenisher therefor generally in an amount of not more than 5 % by weight and preferably not more than 4 % by weight.
  • the developers and replenishers used in the present invention may simultaneously contain a surfactant for the purpose of improving developing properties thereof.
  • surfactants include salts of higher alcohol (C8 ⁇ C22) sulfuric acid esters such as sodium salt of lauryl alcohol sulfate, sodium salt of octyl alcohol sulfate, ammonium salt of lauryl alcohol sulfate, Teepol B-81 (trade mark, available from Shell Chemicals Co., Ltd.) and disodium alkyl sulfates; salts of aliphatic alcohol phosphoric acid esters such as sodium salt of cetyl alcohol phosphate; alkyl aryl sulfonic acid salts such as sodium salt of dodecylbenzene sulfonate, sodium salt of isopropylnaphthalene sulfonate,sodium salt of dinaphthalene disulfonate and sodium salt of metanitrobenzene sulfonate; sulfonic acid salts of alkyl
  • Examples of such compounds are neutral salts such as NaCl, KCl and KBr as disclosed in JP-A- 58- 75 152; chelating agents such as EDTA and NTA as disclosed in JP-A- 58- 190 952 (U.S-A- 4 469 776), complexes such as [Co(NH3)6]Cl3 as disclosed in JP-A- 59- 121 336 (US-A- 4 606 995); ionizable compounds of elements of the group IIa, IIIa or IIIb of the Periodic Table such as those disclosed in JP-A- 55- 25 100; anionic or amphoteric surfactants such as sodium alkyl naphthalene sulfonate and N-tetradecyl-N,N-dihydroxythyl betaine as disclosed in JP-A- 50- 51 324; tetramethyldecyne diol as disclosed in US-A- 4 374 920; non-ionic surfactants as
  • any known means of supplementing a replenisher for developer may be employed.
  • Examples of such methods preferably used are a method for intermittently or continuously supplementing a replenisher as a function of the amount of PS plates processed and time as disclosed in JP-A- 55- 115 039 (GB-A- 2 046 931), a method comprising disposing a sensor for detecting the degree of light-sensitive layer dissolved out in the middle portion of a developing zone and supplementing the replenisher in proportion to the detected degree of the light-sensitive layer dissolved out as disclosed in JN-A- 58- 95 349 (US-A- 4 537 496); a method comprising determining the impedance value of a developer and processing the detected impedance value by a computer to perform supplementation of a replenisher as disclosed in GB-A- 2 208 249.
  • the printing plate of the present invention can also be used in the printing process as a seamless sleeve printing plate.
  • the printing plate is soldered in a cylindrical form by means of a laser.
  • This cylindrical printing plate which has as diameter the diameter of the print cylinder is slided on the print cylinder instead of applying in a classical way a classically formed printing plate. More details on sleeves are given in "Grafisch Nieuws" ed. Keesing, 15, 1995, page 4 to 6.
  • the obtained plate After the development of an image-wise exposed imaging element with an aqueous alkaline solution and drying, the obtained plate can be used as a printing plate as such. However, to improve durability it is still possible to bake said plate at a temperature between 200°C and 300°C for a period of 30 seconds to 5 minutes. Also the imaging element can be subjected to an overall post-exposure to UV-radiation to harden the image in order to increase the run lenght of the printing plate.
  • EXAMPLE 1 Positive working thermal plate based on an alkali-soluble binder.
  • a 0.20 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 mm.
  • 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, posttreated with a solution containing polyvinylphosphonic acid and then with a solution containing aluminum trichloride, subsequently rinsed with demineralized water at 20°C during 120 seconds and dried.
  • This material was imaged with a GERBER C42T TM internal drum platesetter at 12,000 rpm and 2540 dpi.
  • the power level of the laser in the image plane was 6.65 W. After IR-exposure no layer damage, as a result of ablation, could be observed. This was also verified by measuring the optical density of the layer prior and after the IR-laser exposure (see table 1).
  • the lithographic base and the first layer were prepared and coated as described in example 1.
  • the IR_sensitive toplayer was coated from a 1.00% carbon black dispersion (SPECIAL SCHWARZ 250 TM)in methylethylketone/ methoxypropanol 70/30 at 20 ⁇ m wet coating thickness
  • This material was imaged with a GERBER C42TTM internal drum platesetter at 12,000 rpm and 2540 dpi.
  • the power level of the laser in the image plane was 3.5 W. After IR-exposure the top layer is clearly damaged by the IR-laser exposure, even at lower IR-laser power (3.5 W versus 6.65 W for example 1) as a result of ablation processes. On the surface of the layer small dust particles can be observed.
  • EXAMPLE 2 Positive working thermal plate based on an alkali-soluble binder.
  • the lithographic base and the first layer were prepared and coated as described in example 1.
  • This material was imaged with a GERBER C42T TM internal drum platesetter at 12,000 rpm and 2540 dpi.
  • the power level of the laser in the image plane was 6.65 W.
  • After exposure the material was developed in an alkaline developing solution (EP 26 developer commercially available from Agfa), dissolving very rapidly the IR-exposed areas, resulting in a positive working plate.
  • the plate was printed on a Heidelberg GTO46 printing machine with a conventional ink (K+E) and fountain solution (rotamatic), resulting in good prints, i.e.
  • Example Power Gerber C42T Density prior to exposure Density after exposure Example 1 6.65 W 0.34 0.34
  • Example 2 6.65 W 0.19 0.19 Comparative ex 3.5 W 1.19 1.09

Claims (11)

  1. Verfahren zur Herstellung lithografischer Druckplatten mit den nachstehenden Schritten
    a) Bereitstellen eines wärmeempfindlichen Bilderzeugungselements, das auf einer lithografischen Unterlage mit einer hydrophilen Oberfläche eine erste Schicht mit einem in einer wässrigen alkalischen Lösung löslichen Polymeren und auf der gleichen Seite der lithografischen Unterlage wie die erste Schicht eine Deckschicht aufweist, wobei die Deckschicht empfindlich gegenüber Infrarotstrahlung und undurchdringbar für einen SiO2 als Silikat enthaltenden alkalischen Entwickler ist;
    b) bildmäßiges Belichten des wärmeempfindlichen Bilderzeugungselements mit Infrarotstrahlen;
    c) derartiges Entwickeln des bildmäßig belichteten, wärmeempfindlichen Bilderzeugungselements unter Verwendung des alkalischen Entwicklers, dass die belichteten Bereiche der Deckschicht und die unterliegenden Bereiche der ersten Schicht gelöst werden und die nicht belichteten Bereiche der ersten Schicht ungelöst bleiben, dadurch gekennzeichnet, dass die Deckschicht einen IR-Farbstoff in einer Menge von 1 bis 100 Gew.-%, bezogen auf die Gesamtmenge der IR-empfindlichen Deckschicht, enthält, wobei dieser Farbstoff aus der Reihe Indoanilin-, Cyanin-, Merocyanin- und Oxonolfarbstoffe, Porphin-Abkömmlinge, Anthrachinonfarbstoffe, Merostyrylfarbstoffe, Pyrylium-Verbindungen, Diphenylazo- und Triphenylazo-Verbindungen und Squarylium-Abkömmlinge gewählt wird.
  2. Verfahren nach Anspruch 1 zur Herstellung lithografischer Druckplatten mit den nachstehenden Schritten
    a) Bereitstellen eines wärmeempfindlichen Bilderzeugungselements, das auf einer lithografischen Unterlage mit einer hydrophilen Oberfläche eine erste Schicht mit einem in einer wässrigen alkalischen Lösung löslichen Polymeren und auf der gleichen Seite der lithografischen Unterlage wie die erste Schicht eine Deckschicht aufweist, wobei die Deckschicht aus einem Bindemittelharz und einem IR-Farbstoff besteht und für einen SiO2 als Silikat enthaltenden alkalischen Entwickler undurchdringbar ist;
    b) bildmäßiges Belichten des wärmeempfindlichen Bilderzeugungselements mit Infrarotstrahlen;
    c) derartiges Entwickeln des bildmäßig belichteten, wärmeempfindlichen Bilderzeugungselements unter Verwendung des alkalischen Entwicklers, dass die belichteten Bereiche der Deckschicht und die unterliegenden Bereiche der ersten Schicht gelöst werden und die nicht belichteten Bereiche der ersten Schicht ungelöst bleiben, dadurch gekennzeichnet, dass die Deckschicht einen IR-Farbstoff in einer Menge von 1 bis 100 Gew.-%, bezogen auf die Gesamtmenge der IR-empfindlichen Deckschicht, enthält, wobei dieser Farbstoff aus der Reihe Indoanilin-, Cyanin-, Merocyanin- und Oxonolfarbstoffe, Porphin-Abkömmlinge, Anthrachinonfarbstoffe, Merostyrylfarbstoffe, Pyrylium-Verbindungen, Diphenylazo- und Triphenylazo-Verbindungen und Squarylium-Abkömmlinge gewählt wird.
  3. Verfahren zur Herstellung lithografischer Druckplatten nach Anspruch 2, dadurch gekennzeichnet, dass es sich bei dem Bindemittelharz um ein Novolak oder ein Hydroxystyrol enthaltendes Polymeres handelt.
  4. Verfahren zur Herstellung lithografischer Druckplatten nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass es sich bei dem in der ersten Schicht enthaltenen Polymeren um ein hydrophobes Polymeres handelt.
  5. Verfahren zur Herstellung lithografischer Druckplatten nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass es sich bei dem in der ersten Schicht enthaltenen Polymeren um ein Novolak oder ein Hydroxystyrol enthaltendes Polymeres handelt.
  6. Verfahren zur Herstellung lithografischer Druckplatten nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass die erste Schicht eine niedermolekulare Säure enthält.
  7. Verfahren zur Herstellung lithografischer Druckplatten nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass es sich bei der ersten Schicht um eine gegenüber sichtbarer Strahlung und UV-Strahlung desensibilisierte Schicht handelt.
  8. Verfahren zur Herstellung lithografischer Druckplatten nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass die erste Schicht wärmehärtbar ist.
  9. Verfahren zur Herstellung lithografischer Druckplatten nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass es sich bei der lithografischen Unterlage mit einer hydrophilen Oberfläche um einen elektrochemisch gekörnten und anodisierten Aluminiumträger handelt.
  10. Verfahren zur Herstellung lithografischer Druckplatten nach Anspruch 9, dadurch gekennzeichnet, dass der Aluminiumträger mit Polyvinylphosphonsäure behandelt wurde.
  11. Verfahren zur Herstellung lithografischer Druckplatten nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, dass der alkalische Entwickler SiO2 und M2O in einem Molverhältnis von 0,5 bis 1,5 und SiO2 in einer Konzentration von 0,5 bis 5 Gew.-% umfasst.
EP19980203122 1997-10-08 1998-09-16 Verfahren zur Herstellung einer positiv arbeitenden Druckplatte aus einem Wärmeempfindlichen Bildaufzeichnungsmaterial Expired - Lifetime EP0908307B1 (de)

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