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III IIII IIII USOO5595854A United States Patent (19) 11 Patent Number: 5,595,854 Leenders Et Al

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III IIII IIII USOO5595854A United States Patent (19) 11 Patent Number: 5,595,854 Leenders Et Al III IIII IIII USOO5595854A United States Patent (19) 11 Patent Number: 5,595,854 Leenders et al. (45) Date of Patent: *Jan. 21, 1997 54 METHOD FOR THE FORMATION OF HEAT 3,941,596 3/1976 Heiart ...................................... 430/200 MODE MAGE 5,380,607 1/1995 Van Houte et al. .................... 430/200 75 Inventors: Luc Leenders, Herentals; Herman OTHER PUBLICATIONS Uytterhoeven, Bonheiden; Rita Torfs, "Thermal Dye Transfer” by Janssens et al.; Research Dis Herenthout, Leo Oelbrandt, Kruibeke; closure, vol. 320, No. 19, Dec. 1990, Havant GB; p. 931, left Carlo Uyttendaele, Berchem; Jan Van col. last paragraph-right col., second paragraph. den Bogaert, Schilde, all of Belgium Primary Examiner-Richard L. Schilling (73) Assignee: Agfa-Gevaert N.V., Mortsel, Belgium Attorney, Agent, or Firm-Brumbaugh, Graves, Donohue & Raymond * Notice: The term of this patent shall not extend beyond the expiration date of Pat. No. 57 ABSTRACT 5,547,809. A method is disclosed for the formation of a heat mode 21 Appl. No.: 400,345 image comprising the steps of (i) bringing in close contact a donor element, containing a reducing agent and an radia 22 Filed: Mar. 8, 1995 tion to heat converting compound, and an acceptor element, 30 Foreign Application Priority Data containing a reducible organic silver salt, (ii) exposing this assemblage information-wise by intense infra-red laser Mar. 25, 1994 EP European Pat. Off. .............. 94200794. radiation, (iii) peeling apart the elements and (iiii) optionally overall heating the separated acceptor element. (51) int. Cl. .................................................. GO3C 8/08 52 U.S. Cl. .................... ... 430/200; 430/203; 430/964 In a preferred embodiment the laser is an infra-red laser and 58 Field of Search ..................................... 430/200, 201, the radiation to heat converting compound is an infra-red 430/203,964 absorbing compound. 56) References Cited In an alternative embodiment the radiation to heat convert U.S. PATENT DOCUMENTS ing compound is incorporated in the acceptor. 3,218,166 l/1965 Reitter ..................................... 430f2O3 3,767,414 10/1973 Huffman et al. .......................... 96/114 16 Claims, No Drawings 5,595,854 1. 2 METHOD FOR THE FORMATION OF HEAT information-wise exposure thereof to actinic radiation is MODE IMAGE known since quite a while. All these methods are based on the principle of introducing a differentiation properties DESCRIPTION between the exposed and non-exposed parts of the photo polymerizable composition e.g. a difference in solubility, 1. Field of the Invention adhesion, conductivity, refractive index, tackiness, perme The present invention relates to a method for obtaining a ability, diffusibility of incorporated substances e.g. dyes etc. heat mode image. The thus produced differences may be subsequently employed in a dry treatment step to produce a visible image 2. Background of the Invention and/or master for printing e.g. a lithographic or electrostatic Conventional photographic materials based on silver O printing master. halide are used for a large variety of applications. For A difference in solubility between the exposed and non instance, in the pre-press sector of graphic arts rather sen exposed parts of the photopolymerizable composition is sitive camera materials are used for obtaining screened often used for the production of lithographic printing plates images. Scan films are used for producing colour separations where a hydrophilic base is coated with the photopolymer from multicolour originals. Phototype setting materials 15 izable composition, subsequently exposed and developed record the information fed to phototype- and image setters. using a solvent to remove the non-exposed or insufficiently Relative insensitive photographic materials serve as dupli exposed parts. Such a process is for example described in cating materials usually in a contact exposure process. Other "Unconventional imaging processes' by E. Brinckman, G. fields include materials for medical recording, duplicating Delzenne, A. Poot and J. Willems, Focal Press London-New and hard copy, X-ray materials for non-destructive testing, 20 York, first edition 1978, pages 33 to 39. black-and-white and colour materials for amateur- and pro The use of the difference in tackiness to obtain an image fessional still photography and materials for cinemato is described in e.g. U.S. Pat. Nos. 3,060,024, 3,085,488 and graphic recording and printing. 3,649,268. According to the method disclosed in these US Silver halide materials have the advantage of high poten patent applications the image-wise exposed photopolymer tial intrinsic sensitivity and excellent image quality. On the 25 izable composition looses its tackiness in the exposed parts other hand they show the drawback of requiring several wet while the non-exposed parts keep their tackiness. The non processing steps employing chemical ingredients which are exposed parts can therefore be colored with dry dye pig suspect from an ecological point of view. E.g. the commonly ments to make the image visible. used developing agent hydroquinone is a rather unwanted According to the methods described in e.g. U.S. Pat. No. ingredient because of its allergenic effects. The biodegrada 30 3.245,796and EP-A 362,827 the diffusibility of a dye is tion of disposed Phenidone is too slow. Sulphite ions show impeded in the photo-exposed parts of the photopolymeriz a high COD (Chemical Oxygen Demand) and the resulting able composition so that during an overall thermal heating sulphate ions are harmful for e.g. concrete. As a conse Subsequent to photo-exposure dye substances in the non quence it is undesirable that depleted solutions of this kind exposed areas will be able to diffuse to a receptor material. would be discharged into the public sewerage: they have to 35 According to a similar method described in U.S Pat. No. be collected and destroyed by combustion, a cumbersome 4,587,198 the photopolymerizable composition is made and expensive process. impermeable in the exposed parts for a sublimable dye or In the past several proposals have been made for obtain dye-pigment present in a layer adjacent to the layer com ing an imaging element that can be developed using only dry prising the photopolymerizable composition. development steps without the need of processing liquids as 40 According to a method disclosed in U.S. Pat. No. 3,060, it is the case with silver halide photographic materials. 023 the adhesion of the photopolymerizable composition is A dry imaging system known since quite a while is 3M's modified upon image-wise exposure. After image-wise dry silver technology. It is a catalytic process which couples exposure the non-exposed parts will stick or adhere, during a step cf overall heating, to a receiving sheet thus allowing the light-capturing capability of silver halide to the image 45 forming capability of organic silver salts. Traditionally, the transfer of the non-exposed parts to the receiving sheet. silver halide, preferably silver bromide, is formed in situ by As illustrated above photopolymerization can be used in reacting silver behenate with bromide ions. The result of this a variety of methods to reproduce images. Among these process is the formation of very fine grains of silver bro methods several are using dry-developing steps for produc mide, less than 500 angstrons in diameter and positioned in 50 ing the image which is convenient and offers an ecological catalytic proximity to the silver behenate. Exposure to light advantage. However the sensitivity of most photopolymer causes photolytic reduction at the silver bromide crystal izable compositions is rather low so that they are e.g. not (latent image formation) and provides a silver nucleus in suitable for use in exposure with laser light sources which position to permit electron transfer that catalyzes the reduc are recently widely employed for producing images. tion of the organic silver salt to silver metal at an elevated 55 As a further alternative for silver halide chemistry dry temperature thus producing a visual density. A disadvantage imaging elements are known that can be image-wise of this technology that in the non-exposed areas silver halide exposed using an image-wise distribution of heat. These remains which forms print-out silver on aging thereby types of dry imaging elements called heat mode materials increasing the minimal density eventually to an unaccept offer the advantage in addition to an ecological advantage able level for some purposes. Details on the dry silver 60 that they do not need to be handled in a dark room nor any technology can be found in U.S. Pat. Nos. 3,457,075, other protection from ambient light is needed. Heat mode 3,839,049, 4,260,677 and J. Phot. Sci., Vol. 41 (1993), p. recording materials are disclosed in e.g. U.S. Pat. No. 108. 4,123,309, U.S. Pat. No. 4,123,578, U.S. Pat. No. 4,157,412, Another type of non-conventional materials as alternative U.S. Pat. No. 4,547,456 and PCT applications WO 88/04237 for silver halide is constituted by so-called photo mode 65 and WO 93/03928. materials based on photopolymerisation. The use of photo The present invention further extents the teachings on polymerizable compositions for the production of images by heat mode materials. 5,595,854 3 4 It is the object of the present invent to provide a method quinonens, e.g., 2-methyl-5-(1-phenyl-5tetrazolylthio) for the formation of a heat mode image involving only dry hydroquinone, 5-pyrazolones, 3-pyrazolones,
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