EP1588847B1 - Method for accurate exposure of small dots on a heat-sensitive positive-working lithographic plate material - Google Patents

Method for accurate exposure of small dots on a heat-sensitive positive-working lithographic plate material Download PDF

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Publication number
EP1588847B1
EP1588847B1 EP20040101647 EP04101647A EP1588847B1 EP 1588847 B1 EP1588847 B1 EP 1588847B1 EP 20040101647 EP20040101647 EP 20040101647 EP 04101647 A EP04101647 A EP 04101647A EP 1588847 B1 EP1588847 B1 EP 1588847B1
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EP
European Patent Office
Prior art keywords
coating
energy density
image
plate
infrared light
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German (de)
English (en)
French (fr)
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EP1588847A1 (en
Inventor
Joan c/o AGFA-GEVAERT Vermeersch
Wim c/o Agfa-Gevaert Sap
Marc c/o Agfa-Gevaert Van Damme
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Agfa NV
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Agfa Graphics NV
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Priority to EP20040101647 priority Critical patent/EP1588847B1/en
Priority to DE200460006378 priority patent/DE602004006378T2/de
Priority to JP2005121405A priority patent/JP4731197B2/ja
Priority to US11/114,210 priority patent/US7467587B2/en
Priority to CN 200510067607 priority patent/CN1689802B/zh
Publication of EP1588847A1 publication Critical patent/EP1588847A1/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C1/00—Forme preparation
    • B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
    • B41C1/1083—Mechanical aspects of off-press plate preparation

Definitions

  • the present invention relates to a direct-to-plate exposure method for making lithographic printing plates from a heat-sensitive positive-working precursor, more particularly to a method that enables the accurate exposure of small dots as required in stochastic screens and in amplitude-modulated screens having high rulings.
  • 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.
  • a typical positive-working plate precursor comprises a hydrophilic support and an oleophilic coating which is not readily soluble in an aqueous alkaline developer in the non-exposed state and becomes soluble in the developer after exposure to radiation.
  • heat-sensitive printing plate precursors have become very popular. Such thermal materials offer the advantage of daylight stability and are especially used in the so-called computer-to-plate method (CtP) wherein the plate precursor is directly exposed, i.e. without the use of a film mask.
  • the material is exposed to heat or to infrared 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 or by increasing the penetrability of a development barrier layer.
  • 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 or by increasing the penetrability of a development barrier layer.
  • thermal plates form an image by a heat-induced solubility difference in an alkaline developer between exposed and non-exposed areas of the coating.
  • the coating typically comprises an oleophilic binder, e.g. a phenolic resin, of which the rate of dissolution in the developer is either reduced (negative working) or increased (positive working) by the image-wise exposure.
  • the solubility differential leads to the removal of the non-image (non-printing) areas of the coating, thereby revealing the hydrophilic support, while the image (printing) areas of the coating remain on the support.
  • positive-working thermal plate materials are described in e.g. EP-A 625728, 823327, 825927, 864420, 894622 and 901902.
  • the quality of at least part of the image relies on the accurate reproduction of small dots.
  • Such print jobs require extremely tight control of the entire plate-making and printing process taking into account phenomena such as dot gain on the printing press.
  • AM screens are further characterized by their line frequency, also called screen ruling, which equals the number of lines of dots per unit of distance, universally expressed as lines per inch (lpi).
  • the high quality AM images used in the method of the present invention require a screen ruling of not less than 150 lpi (about 60 lines/cm), more preferably not less than 200 lpi (about 80 lines/cm).
  • a 1% dot corresponds to a printing area that occupies 1% of the halftone cell, i.e. a dot having a diameter of about 20 ⁇ m.
  • halftone images are generally exposed on a thermal plate material by means of infrared light in a digital imagesetter.
  • the imagesetter has an output resolution, universally expressed in terms of imaging spots or pixels per inch (ppi), that is much higher than the screen ruling.
  • a so-called raster image processor (RIP) translates the halftone image information into image recording information, which may be visualized by overlaying the halftone cells of the halftone image grid over the image-recording spots of the imagesetter resolution grid ( Figure 1).
  • the number of pixels per halftone cell is 64 (8x8), but in practice that number is much higher.
  • FM screening frequency-modulated screening
  • first-order FM screens consist of variably spaced dots of a small, fixed size, called microdots.
  • a typical FM screened image consists of microdots having a size of 25 ⁇ m or less. The minimum size of the microdots is limited only by the output resolution of the imagesetter.
  • FM microdots can be as small as a single imagesetter pixel, singe-pixel dots may actually be too small to be practical, so often FM microdots are built from cells of 1x1, 2x2 or 3x3 imagesetter pixels.
  • a microdot size of 20 ⁇ m may be used - about as large as a 1% dot in a 150 lpi AM screen - which can be exposed on the plate by means of four (2x2) pixels of 10 ⁇ m each. Since the microdots are dispersed across the screen by varying their frequency in accordance with the image tone value, concepts such as screen ruling do not apply in FM screening.
  • FM screening vs. AM screening
  • AM screening may cause problems such as a 'flat' appearance of light skin tones and wood tones or excessively grainy highlights ( ⁇ 10% tones). Therefore, variants have been developed such as second-order stochastic screening which combines the concept of variable dot size with variable spacing.
  • second-order stochastic screening which combines the concept of variable dot size with variable spacing.
  • hybrid screening wherein stochastic dot patterns are used for some portions of the image and conventional AM halftoning for other portions.
  • the areas of the coating of the plate precursor that correspond to the non-printing areas are exposed and washed away in a developer.
  • the temperature that is induced in the coating during heat-mode exposure e.g. using an infrared laser, is dependent on the energy density (expressed in Joules per area, e.g. mJ/cm 2 ) of the laser beam at the surface of the plate.
  • Thermal plates are characterized by a threshold temperature above which the imaging mechanism of the coating is triggered.
  • a commercially available method for determining a suitable energy density for the practical exposure of a thermal plate relies on checkerboard matching and will be explained hereafter.
  • a 50% halftone image is exposed on the plate using various checkerboard patterns wherein the edges of the dots just touch each other, as shown in Figure 2.
  • the images in this figure correspond to a so-called square spot, but the same principles can be used for other spot forms such as circular or elliptical spots.
  • any reference to 'dot size' and 'spot size' shall be understood as a reference to the diameter in case of a circular dot/spot, the long axis of an elliptical or rectangular dot/spot and the edge of a square dot/spot.
  • a square spot may be generated on the plate by sweeping a narrow rectangular laser spot in the direction transverse to the long axis of the rectangular spot as described in US 6,121,996.
  • the small dots of the 1x1 checkerboard correspond to a single square spot of the imagesetter.
  • a 2x2 checkerboard consists of dots which have twice the size of the spot, etc.
  • the dot area obtained on the plate after exposure of such 50% checkerboard patterns as shown in Figure 2 and development should be 50%, irrespective of the dot size.
  • Figure 3 shows the actual dot area, measured by means of a reflection densitometer and calculated according to the above formula, obtained on a plate exposed with a 50% checkerboard pattern at various energy density values and then processed according to the conditions (time, temperature, developer) used.
  • Figure 3 shows that when these 50% checkerboard patterns are exposed at low energy densities, the dot area on the plate is larger than the target value of 50% : it is believed that, due to the underexposure, the coating just around the edge of the dot does not dissolve sufficiently rapidly in the developer. At too high energy density values, the overexposure of the coating around the dot leads to dissolution of the edges of the dot, resulting in a dot area value that is lower than 50%.
  • the curve shown in Figure 3 can be used for determining the energy density value for the practical exposure of a positive-working thermal plate. From these curves, it can be established by interpolation at which energy density the obtained dot area coincides with the target value (50%) : that value is referred to herein as the 'right exposure energy density' (REED) .
  • the REED value is defined as the minimum energy density at which the dot area on the plate, occupied by an image corresponding to a 50% halftone in the image data, coincides with the 50% target value. It is clear to the skilled person that a lower REED value indicates a higher sensitivity of the plate.
  • Figure 3 shows that the REED value for the 1x1 checkerboard (10 ⁇ m dots), obtained by the above described method, is about 285 mJ/cm 2 .
  • the present inventors have now established that the thus obtained REED value only produces good prints for AM screens at medium to low frequency (i.e. wherein 1% dots have a size >25 ⁇ m). It is observed that the REED value thus obtained is not suitable for the high-quality screens which are used in the method of the present invention, i.e. images comprising microdots having a size ⁇ 25 ⁇ m : positive-working thermal plates which are exposed at the REED, obtained by the above method, produce prints wherein these small dots are partially or completely lost. The inventors believe that the REED value, which is obtained with conventional methods such as reflectance densitometry explained above, is too high and results in an overexposure of the non-printing area that surrounds the microdot.
  • the actual i.e. physical size of the resulting microdot is smaller than intended although the reflection density measurements suggest that exposure at the REED produces a dot size on the plate that is equal to the image dot size in the RIP.
  • the error is noticed on the printed copies because the final ink dot on the printed copy is the result of the physical dot on the plate (in this discussion, the so-called 'mechanical dot gain' on the press due to ink spreading in the paper is ignored, since this phenomenon is routinely compensated by the software of the imagesetter).
  • optical dot size is related to the densitometers which are typically used in these commercially available methods : the reflection density of the plate is measured by means of a densitometer of which the spot size is much larger than the true size of the dots present in the checkerboard image. Due to light scattering and halo-effects at the edge of the microdots, such measurements produce optical dot area values that are higher than the true physical dot area which can be determined by e.g. scanning electron microscopy (SEM, see e.g. Fig. 6) or microdensitometry (further explained in the Examples section).
  • SEM scanning electron microscopy
  • Fig. 6 microdensitometry
  • This 'optical dot gain' phenomenon is more significant at small dot sizes, because it is an edge effect : a fine pattern such as a 10 ⁇ m checkerboard has more edges than a coarse pattern such as a 60 ⁇ m checkerboard.
  • the REED value as obtained by the known methods using a conventional densitometer which we will refer to as the 'optical REED', is indeed the 'right' exposure energy density for images consisting of relatively large dots such as 60 ⁇ m dots, but not for high-quality images comprising microdots having a dot size ⁇ 25 ⁇ m. Due to the optical dot gain phenomenon described above, the loss of small image dots is incorrectly measured by the conventional methods and only detected when the printed copies appear to be too low in density.
  • the 'physical REED' which is defined as the energy density at which the physical area on the plate, occupied by a microdot corresponding to a 50% halftone in the image data, coincides with the 50% target value.
  • the physical REED is obtained by means of measuring techniques that produce the true, physical dot area on the plate, such as SEM or microdensitometry, whereas the optical REED is obtained by means of conventional, 'macroscopic' densitometry, i.e.
  • Figure 4 shows the physical dot area values obtained by microdensitometry vs. energy density for the same sample and 50% checkerboard patterns as in Figure 3. It is clear that the physical REED, i.e. the energy density where the curves in Figure 4 coincide with the 50% target value, is substantially lower than the optical REED obtained in Figure 3 (about 115 mJ/cm 2 vs. 285 mJ/cm 2 for the 1x1 pattern).
  • the method is explained with reference to Figure 5 wherein these energy density values form a series of discrete values resulting in a step-wedge, but it should be clear to the skilled reader that the energy density values may also vary continuously so as to obtain a continuous wedge.
  • a preferred continuous wedge varies by not more than 10 mJ/cm 2 per cm wedge length.
  • the solid step-wedge of Figure 5 comprises only 7 steps, wherein each step is formed by 64 (8x8) imagesetter pixels. All pixels in each step are exposed at the same energy density (step 1 : 60 mJ/cm 2 ; step 2 : 80 mJ/cm 2 ; etc. upto step 7 : 180 mJ/cm 2 ).
  • the steps are preferably much larger, having dimensions which are sufficiently large to enable density measurements of each step with macroscopic reflectance densitometers as in the conventional methods described above.
  • a representation of such a practical embodiment would not allow to show the many imagesetter pixels contained in each step.
  • the wedge is preferably generated by the software that controls the imagesetter, although similar results can be obtained by other means, e.g. by placing a wedge filter in the light path of the imagesetter, preferably in contact with the plate.
  • the minimum and maximum energy density for exposing the wedge should be adjusted to the particular type of plate that is being tested.
  • a suitable interval may range from 30 to 300 mJ/cm 2 .
  • the number of steps in a preferred step-wedge is preferably higher than in Figure 5 so as to allow a precise determination of the clearing point, which will now be explained.
  • the coating normally remains on the support completely, i.e. the optical density of the coating essentially equals D u , the optical density of the unexposed plate.
  • the temperature in the coating approaches and eventually exceeds the threshold temperature and, as a result, the density of the coating that remains on the plate after processing decreases.
  • CP can be determined with a step-wedge exposure by plotting the discrete values of optical density of the exposed and processed plate vs. the energy density as shown in Figure 5 and establishing by interpolation at which energy density the optical density of the coating is reduced by 95%.
  • the physical REED lies in the range between the clearing point and the energy density equal to 1.5 times the clearing point.
  • the plate/platesetter/developer system of Example 6 below is characterized by a physical REED of about 115 mJ/cm 2 for the three nxn patterns, which is 15% higher than the clearing point (100 mJ/cm 2 ).
  • the present invention enables to expose high-quality halftone images comprising microdots having a size ⁇ 25 ⁇ m accurately on a positive-working thermal plate by using an energy density which is in the range from CP to 1.5*CP.
  • the 1x1 (10 ⁇ m) checkerboard image shown in Fig.6 illustrates that for some plates it may be beneficial to use an energy density in the lower part of the range from CP to 1.5*CP : this image has been exposed at 1.4*CP, which is sufficiently low to prevent loss of the complete dot, but it is clear that the physical dot area is less than 50% (the dark unexposed microdots occupy less area than the light non-printing areas where the exposure has rendered the coating soluble in the developer and the grainy surface of the aluminium substrate has been revealed).
  • Exposure according to the preferred embodiment i.e. at an energy density from CP to 1.3*CP, may therefore produce a physical dot area that is closer to the 50% target value than the exopsure in the subrange from 1.3*CP to 1.5*CP.
  • the energy density may even be in the range from CP to 1.2*CP, from CP to 1.1*CP or be essentially equal to CP.
  • the halftone image exposed on the plate may also comprise microdots having a size ⁇ 20 ⁇ m and even ⁇ 15 ⁇ m, e.g. in the range between 10 and 15 ⁇ m.
  • the image may contain more than 10%, more preferably more than 20% and most preferably more than 30% of such microdots.
  • first-order FM screening the entire image consists of such microdots.
  • the method of the present invention also produces excellent results for the exposure of second-order FM images, as well as images obtained by hybrid screening methods and high-quality AM-screened images, i.e. AM screens having a ruling of not less than 150 lpi (about 60 lines/cm), more preferably not less than 200 lpi (about 80 lines/cm).
  • AM screening is Agfa Balanced Screening, trademark of Agfa-Gevaert, Belgium.
  • Preferred FM screening methods for generating the halftone image are e.g. the commercially available products CrystalRaster, Sublima (both trademarks of Agfa-Gevaert, Belgium) and Staccato (trademark of Creo, Canada).
  • Sublima is a hybdrid method generating FM dots in the highlights and shadows of a picture but AM dots in the midtones.
  • the present invention also provides a method for calibrating a lithographic plate-making system comprising (i) an imagesetter, (ii) a positive-working heat-sensitive lithographic printing plate precursor comprising a support and a coating provided thereon and (iii) a developer, the method comprising the steps of
  • the heat-sensitive lithographic printing plate precursors which are suitable for the method of the present invention typically contain a hydrophilic support and a hydrophobic coating provided thereon comprising an infrared light-to-heat converter such as an infrared dye or pigment and a binder which is soluble in an aqueous alkaline developer.
  • 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.
  • a preferred support is a metal support such as aluminum or stainless steel.
  • the metal can also be laminated to 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 coating which is provided on the support, may consist of one or more layer(s).
  • additional layers besides the layer(s) which comprise the alkali-soluble binder or the layer(s) which comprise the infrared light-to-heat converter are e.g. a "subbing" layer which improves the adhesion of the coating to the support and a covering layer which protects the coating against contamination or mechanical damage.
  • the alkali-soluble binder can be present in one or more layer(s) of the coating.
  • 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 non-volatile components of the coating.
  • the alkali-soluble binder is preferably an organic polymer which has 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.
  • 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 alkali-soluble binder is a phenolic resin wherein the phenyl group or the hydroxy group of the phenolic monomeric unit are chemically modified with an organic substituent.
  • the phenolic resins which are chemically modified with an organic substituent may exhibit an increased chemical resistance against printing chemicals such as fountain solutions or press chemicals such as plate cleaners. Examples of preferred chemically modified phenolic resins are described in EP-A 0 934 822, EP-A 0 996 869, EP-A 1 072 432, US 5,641,608, EP-A 0 982 123, WO99/01795, EP-A 933682, EP-A 894622 and WO 99/63407 and in unpublished European patent application nos. 02 102 446, 02 102 444, 02 102 445, 02 102 443, all filed on 15.10.2002 and no. 03 102 522, filed on 13.08.2003.
  • the dissolution behavior of the coating 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 layer(s) which comprise(s) the alkali-soluble binder 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 coating.
  • 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.
  • Examples of the phenols 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, 3,4,5-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 reversed by heating, so that the dissolution of the exposed areas is not substantially delayed and a large dissolution differential between exposed and unexposed areas can thereby be obtained.
  • developer resistance means can be added to a layer comprising the alkali-soluble binder or to another layer of the coating.
  • Inhibitors of this type typically comprise at least one 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.
  • Suitable inhibitors improve the developer resistance because they delay the penetration of the aqueous alkaline developer into the coating.
  • Such compounds can be present in the layer(s) comprising the alkali-soluble binder, as described in e.g. EP-A 950 518, and/or in a development barrier layer on top of said layer, as described in e.g. EP-A 864 420, EP-A 950 517, WO 99/21725 and WO 01/45958.
  • the solubility of the barrier layer in the developer or the penetrability of the barrier layer by the developer can be increased by exposure to heat or infrared light.
  • inhibitors which delay the penetration of the aqueous alkaline developer into the coating include the following :
  • the above mentioned inhibitor of type (b) and (c) tends to position itself, due to its bifunctional structure, 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 layer comprising the alkali-soluble binder.
  • the surfactants also act as a spreading agent which improves the coating quality.
  • the separate top layer thus formed seems to be capable of acting as the above mentioned barrier layer which delays the penetration of the developer into the coating.
  • the inhibitor of type (a) to (c) can be applied in a separate solution, coated on top of the layer(s) comprising the alkali-soluble binder.
  • 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 or hydrophobic phase is obtained at the top of the coating which is capable of acting as the above mentioned development barrier layer.
  • the infrared light absorbing dye or pigment may be present in the same layer(s) as the alkali-soluble binder, in the optional barrier layer discussed above and/or in an optional other layer.
  • the IR absorber is concentrated in or near the barrier layer, e.g. in an intermediate layer between the alkali-soluble binder and the barrier layer.
  • said intermediate layer comprises the IR absorbing compound in an amount higher than the amount of IR absorbing compound in the alkali-soluble binder or in the barrier layer.
  • Preferred IR absorbing dyes are cyanine dyes, merocyanine dyes, indoaniline dyes, oxonol dyes, pyrilium dyes and squarilium dyes.
  • IR dyes examples include IR dyes, IR dyes, and IR dyes.
  • IR dyes examples include IR dyes, IR dyes, and IR dyes.
  • a preferred compound is the following cyanine dye : The preferred amount of this dye is less than 40 mg/m 2 .
  • the protective layer generally comprises at least one water-soluble 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 layer(s) comprising the alkali-soluble binder may further contain additional ingredients.
  • 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.
  • contrast dyes are the amino-substituted tri- or diarylmethane dyes, e.g. crystal violet, methyl violet, victoria pure blue, flexoblau 630, basonylblau 640, auramine and malachite green.
  • the dyes which are discussed in depth in the detailed description of EP-A 400706 are suitable contrast dyes.
  • Surfactants especially perfluoro surfactants, silicon or titanium dioxide particles, polymers particles such as matting agents and spacers are also well-known components of lithographic coatings.
  • 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 optimised.
  • 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. Also infrared lamps can be used.
  • the drying time may typically be 15-600 seconds.
  • a heat treatment and subsequent cooling may provide additional benefits, as described in WO99/21715, EP-A 1074386, EP-A 1074889, WO00/29214, and unpublished Eur. patent application nos. 02102413, 02102414, 02102415, filed on 04.10.2002.
  • the plate precursor 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 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 plate precursor 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 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, more preferably 750 to 1100 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 plate precursor, 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 : 5-25 ⁇ 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.
  • An XTD platesetter equipped with one or more laserdiodes emitting in the wavelength range between 750 and 850 nm is an especially preferred embodiment for the method of the present invention.
  • 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 formation of the lithographic image by the plate precursor 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 believed to be a kinetic rather than a thermodynamic effect, i.e. the non-image areas are characterized by a faster dissolution in the developer than the image-areas.
  • the underlying hydrophilic surface of the support is revealed at the non-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 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. During development, 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 developer may further contain compounds which increase the developer resistance of the non-image areas, e.g. a polyalcohol such as sorbitol, preferably in a concentration of at least 40 g/l, and/or a poly(alkylene oxide) containing compound such as e.g. Supronic B25, commercially available from RODIA, preferably in a concentration of at most 0.15 g/l.
  • 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 plate precursor.
  • the addition can be regulated, for example, by measuring the conductivity as described in EP-A 0 556 690.
  • the processing of the plate precursor may also comprise a rinsing step, a drying step and/or a gumming step.
  • the plate precursor can, if required, be post-treated with a suitable correcting agent or preservative as known in the art.
  • the layer can be briefly heated to elevated temperatures ("baking").
  • 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.
  • Suitable single-fluid inks 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.
  • thermo-resist for forming a pattern on a substrate by direct imaging techniques, e.g. in a PCB (printed circuit board) application as described in US 2003/0003406 A1.
  • the following coating solution was prepared : Parts (grams) Dowanol PM (1) 389.06 Methyl ethyl ketone 262.20 Tetrahydrofuran 206.40 Alnovol SPN452 (2) 132.50 3,4,5-trimethoxy cinnamic acid 7.29 S0094 (3) 1.50 Basonylblau 640 0.54 TegoGlide 410 0.52 (1)1-methoxy-2-propanol from Dow Chemical Company. (2) Alnovol SPN452 is a 40.4 wt.% solution of novolac in Dowanol PM (commercially available from Clariant). (3)S0094 is an IR absorbing cyanine dye commercially available from FEW Chemicals.
  • S0094 has the chemical structure IR-1 shown above.
  • (4)Basonyl Blue 640 is a quaternized triarylmethane dye commercially available from BASF.
  • (5)TegoGlide 410 is a 10 wt.% dispersion in water of a block-co-polysiloxane/poly(alkylene oxide) surfactant commercially available from Tego Chemie Service GmbH.
  • Dowanol PM (defined above) 330.04 Methyl ethyl ketone 267.99 Tetrahydrofuran 210.16 20 wt.% solution of POL-01 (1) in Dowanol PM 158.03 DURITE SD126A (2) 10.54 S0094 (defined above) 1.52 TegoGlide 410 (defined above) diluted 1:10 with Dowanol PM 21.72 (1)
  • POL-01 is a chemically modified novolac, prepared as follows: - Preparation of the diazonium solution: A mixture of 2.6 g AM-10 and 25 ml acetic acid and 37.5 ml water was cooled to 15°C.
  • AM-10 is a compound having the following chemical structure: - Preparation of the phenolic polymer solution: A mixture of 45.9 g ALNOVOL SPN452 (Alnovol SPN452 is a solution of a novolac resin, 40 % by weight in Dowanol PM, obtained from Clariant GmbH), 16.3 g NaOAc.3H 2 O and 200 ml 1-methoxy-2-propanol was stirred and cooled to 10°C.
  • the above solutions were coated on a conventional grained and anodized aluminium support at a wet coating thickness of 26 ⁇ m and dried.
  • the dry coating weight was 1.47 g/m 2 .
  • the plates were aged in a warehouse during 5 days at 50°C.
  • optical REED and physical REED values of the above systems was determined as explained above by exposing nxn checkerboard patterns at various energy densities and establishing at which energy density the dot coverage, obtained from 'marcroscopic' and 'microscopic' densitometry and the Murray-Davies equation defined above, was equal to 50%.
  • the 'macroscopic' reflection density was obtained with a GretagMacbeth D19C 47B/P densitometer, commercially available from Gretag - Macbeth AG.
  • Such conventional densitometers are typically equipped with several filters (e.g. cyan, magenta, yellow) : the optical density was measured with the filter that corresponds to the color of the coating, e.g. a cyan filter is preferably used for measuring the optical density of a blue colored coating. All optical density values were measured with reference to the uncoated support of the plate.
  • the clearing point was obtained by exposing a step wedge with fixed intervals of 10 mJ/cm 2 on the plates with the above defined exposure devices and using the above defined GretagMacbeth densitometer for measuring the optical density in each step of the exposed coating after processing. All plates provided clear prints without toning (i.e. no ink acceptance in the exposed areas) at the clearing point, i.e. exposed with the energy density that reduces the optical density of the coating to 0.05*D u .
  • Table 1 lists the optical dot area values of the six systems, exposed with a 1x1, 2x2 and 6x6 checkerboard pattern at various energy densities.
  • Table 1 Example 1
  • Example 2 Example 3 Energy density (mJ/cm 2 )
  • Optical dot area Energy density (mJ/cm 2 ) Optical dot area 1x1 2x2 6x6 1x1 2x2 6x6 1x1 2x2 6x6 60 80 71 61 85 95 90 76 93 83 69 80 70 63 56 95 93 87 59.5 85 89 77 64 100 65 61 55 105 90 81 58.5 95 83 72 61 120 59 58 54 114 86 77 55.5 105 77 68 60 140 55 56 54 124 83 74 54.5 114 69 64 57 160 51 54 53 133 77 69 53.5 133 52 57 55 180 47 52 52 143 73 67 53
  • Table 2 lists the physical dot area values of the six systems, exposed with a 1x1, 2x2 and 6x6 checkerboard pattern at various energy densities.
  • Table 2 Example 1
  • Example 2 Example 3 Energy density (mJ/cm 2 ) Physical dot area Energy density (mJ/cm 2 ) Physical dot area Energy density (mJ/cm 2 ) Physical dot area 1x1 2x2 6x6 1x1 2x2 6x6 1x1 2x2 6x6 60 51.0 57.0 52.0 105 56.0 76 70.0 66.0 56.0 80 53.0 51.0 49.5 114 53.5 85 61.0 56.0 51.0 100 47.5 46.5 49.0 124 58.0 53.0 95 54.5 52.0 50.0 120 40.5 40.5 48.0 133 52.0 52.0 105 48.5 48.0 48.5 140 37.5 37.5 47.5 143 50.0 50.5 114 40.0 43.0 47.0 153 47.5 49.5 162 46.5 49.5
  • Example 4 Example 5
  • Example 6 Energy density (mJ/

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Materials For Photolithography (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
  • Printing Plates And Materials Therefor (AREA)
EP20040101647 2004-04-21 2004-04-21 Method for accurate exposure of small dots on a heat-sensitive positive-working lithographic plate material Expired - Lifetime EP1588847B1 (en)

Priority Applications (5)

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EP20040101647 EP1588847B1 (en) 2004-04-21 2004-04-21 Method for accurate exposure of small dots on a heat-sensitive positive-working lithographic plate material
DE200460006378 DE602004006378T2 (de) 2004-04-21 2004-04-21 Verfahren zur genauen Belichtung von kleinen Punkten auf eine Wärmeempfindliche positiv arbeitende Flachdruckplatte
JP2005121405A JP4731197B2 (ja) 2004-04-21 2005-04-19 感熱性のポジ作用性平版材料における小ドットの正確な露出方法
US11/114,210 US7467587B2 (en) 2004-04-21 2005-04-21 Method for accurate exposure of small dots on a heat-sensitive positive-working lithographic printing plate material
CN 200510067607 CN1689802B (zh) 2004-04-21 2005-04-21 在热敏正性石印印版材料上精确曝光小网点的方法

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EP1884372B1 (en) 2006-08-03 2009-10-21 Agfa Graphics N.V. A lithographic printing plate support
KR101777834B1 (ko) * 2009-03-04 2017-09-26 씨씨엘 씨큐어 피티와이 엘티디 렌즈어레이의 제조방법의 개량
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JP3814961B2 (ja) * 1996-08-06 2006-08-30 三菱化学株式会社 ポジ型感光性印刷版
DE69714197T2 (de) * 1996-12-11 2003-02-13 Agfa-Gevaert, Mortsel Sichtbarer Kontrollstreifen für Abbildungsmedien
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JP2002062660A (ja) * 2000-08-16 2002-02-28 Fuji Photo Film Co Ltd 平版印刷版原版
JP2002296790A (ja) * 2001-03-30 2002-10-09 Fuji Photo Film Co Ltd 平版印刷版原版
JP2003098684A (ja) * 2001-09-21 2003-04-04 Fuji Photo Film Co Ltd 画像評価方法及び平版印刷版の品質管理方法
EP1295717B1 (en) * 2001-09-24 2007-07-25 Agfa Graphics N.V. Heat-sensitive positive-working lithographic printing plate precursor
JP2003228164A (ja) * 2002-02-06 2003-08-15 Fuji Photo Film Co Ltd 平版印刷版用原版
JP2004029680A (ja) * 2002-06-28 2004-01-29 Fuji Photo Film Co Ltd 平版印刷版用原板
EP1380417B1 (en) * 2002-07-03 2006-08-23 Agfa-Gevaert Positive-working lithographic printing plate precursor
EP1401190B1 (en) * 2002-09-17 2013-05-29 Agfa Graphics N.V. Sub dot phase modulation for computer to plate inkjet system
JP4473262B2 (ja) * 2003-03-14 2010-06-02 コダック グラフィック コミュニケーションズ カナダ カンパニー 放射線感受性素子の現像性促進
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CN1689802A (zh) 2005-11-02
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DE602004006378T2 (de) 2008-01-10
JP4731197B2 (ja) 2011-07-20
JP2005309439A (ja) 2005-11-04

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