EP0003263B1 - Méthode pour l'obtention d'une image et élément pour la formation d'une image par inhibition à base de complexes de cobalt (III) - Google Patents

Méthode pour l'obtention d'une image et élément pour la formation d'une image par inhibition à base de complexes de cobalt (III) Download PDF

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EP0003263B1
EP0003263B1 EP19780300914 EP78300914A EP0003263B1 EP 0003263 B1 EP0003263 B1 EP 0003263B1 EP 19780300914 EP19780300914 EP 19780300914 EP 78300914 A EP78300914 A EP 78300914A EP 0003263 B1 EP0003263 B1 EP 0003263B1
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image
photoinhibitor
cobalt
imaging element
precursor composition
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EP0003263A1 (fr
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Anthony Adin
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Eastman Kodak Co
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Eastman Kodak Co
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/67—Compositions containing cobalt salts or cobalt compounds as photosensitive substances
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/56—Processes using photosensitive compositions covered by the groups G03C1/64 - G03C1/72 or agents therefor

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  • This invention relates to a cobalt(III) complex-containing photographic element which can be made negative-working or positive-working, depending upon the nature of the exposure given.
  • Cobalt(lll) complexes containing releasable ligands have been utilized in non-silver redox reactions photoinitiated by means of photoreductants or spectral sensitizers, as disclosed, for example, in Research Disclosure, Volumes 126 and 130, October 1974 and February 1975, Publications Nos. 12617 and 13023, respectively, published by Industrial Opportunities Limited, Homewell, Havant, Hampshire P091 EF, United Kingdom.
  • Preferred reduction products of such a reaction are cobalt(II) and amines or ammonia.
  • Either of these can in turn be used to form images, the cobalt (II) being chelated by compounds capable of forming at least bidentate chelates, or the amines being reacted with dye precursors, including diazo-coupler systems, to form a dye; or the cobalt(II) or amines can be used to bleach out preincorporated dye.
  • imaging processes are disclosed in Research Disclosure, Volume 126, October 1974, Publication No. 12617, part lll.
  • Amplification can be achieved by using a reduction agent precursor capable of forming a reducing agent with the aforesaid reduction products, for the reduction of remaining cobalt(lll) complexes.
  • certain of said chelating compounds for cobalt(II) form, when chelated, a reducing agent, as described in Research Disclosure, Volume 135, July 1975, Publication No. 13505, and o-phthalaldehyde will react with ammonia to form a reducing agent, as disclosed in Research Disclosure, Volume 158, June 1977, Publication No. 15874.
  • Imaging elements based upon such reactions involving cobalt(lll) complexes are useful, for example, in graphic arts as room-light handling contact films, e.g., as an intermediate in the preparation of printing plates.
  • the cobalt complex imaging elements of the prior Research Disclosures can be either negative-working or positive-working, but the same element is not both. That is, a separate image-forming material (e.g., a dye former) is used in those instances in which the element is to be negative-working, compared to those instances in which the element is positive-working (e.g., by bleaching out a pre-existing dye). It would be highly desirable to provide an imaging element wherein the same element can be made negative or positive working, merely by controlling the processing of the element.
  • a separate image-forming material e.g., a dye former
  • a further aspect of said prior cobalt complex imaging elements is that they can develop background print-up because the unexposed photoinitiator in the background areas causes increased D min (minimum density) upon handling as a result of room light activation of the photoinitiator.
  • D min minimum density
  • a peel-apart system can be used, that is, one wherein the layer of cobalt(III) complex relied upon for the imaging is removed from the image recording layer. Print-up is more difficult to avoid in integral systems, particularly when the exposed photo-reductant reduces the complex at room temperatures.
  • Metal complexes capable of releasing amines have been used prior to this invention to thermally activate image recording means such as diazo-coupler compositions. Examples are disclosed in U.S. Patent Nos. 3,469,984; 3,224,878; and 2,774,669. Because of their thermal instability, such complexes generate amines when overall heated, to cause diazo coupling or the like. There is no disclosure in this art of means for inhibiting such dye development.
  • Patents relating to the background of image formation using amines or cobalt complexes include U.S. Patents Nos. 2,774,669; 3,102,811; 3.469,984; 3,2?4,878; and Japanese Patent Publication No. 74/6234.
  • United Kingdom Patent No. 1,497,452 discloses the use of a cobalt complex and a photoreductant which may include an image-former.
  • a layer containing such a composition may be coated on a support using a chlorinated hydrocarbon solvent.
  • the method of forming an image comprising first exposing an imaging element containing a layer of an energy-activatable image precursor composition comprising at least one cobalt III complex having ligands releasable by said activating energy, said energy-activatable image precursor being a composition activatable by electromagnetic energy of any kind in areas where it has not been inhibited by an already exposed photoinhibitor, as hereinafter described, and said composition when activated by exposure to electromagnetic energy providing an image either by generating a density or by destroying a pre-existing density or altering its colour, and before or after said first exposure placing the layer of the energy-activatable image precursor composition in contact with a layer of an image-forming material which generates an image in response to the release of the ligands and which contains, as a photoinhibitor, a single compound or a mixture of compounds which does not form a complex with cobalt and which responds to activating radiation having a wavelength greater than 300 nm, different from that activating
  • This invention relates to an imaging process wherein an imagwise exposure activates an image precursor composition comprising at least a cobalt(lll) complex containing releasable ligands, to form an image, and wherein a second exposure photolytically generates the means for inhibiting such ligand release. More specifically, it has been discovered that a photoinhibitor such as a photolytic acid generator after suitable exposure will inhibit the release of ligands which would otherwise occur by activating the exposure of the image precursor composition.
  • a photoinhibitor such as a photolytic acid generator after suitable exposure will inhibit the release of ligands which would otherwise occur by activating the exposure of the image precursor composition.
  • an “image precursor composition”, as used herein, is a composition as described which when appropriately activated by exposure, produces an image either by generating a density or by destroying a pre-existing density or altering its colour.
  • the precursor composition is "energy-activatable” if it is activatable by electromagnetic energy of any kind in areas where it is not inhibited by an already exposed photoinhibitor of the invention.
  • the image precursor composition can be activated by thermal or light exposures of the type disclosed, for example, in Research Disclosure, Volume 147, July 1976, Publication No. 14719 depending upon the circumstances. Thermal exposure can occur through the use of infrared radiation or convection, but preferably it is achieved through conduction. As will be readily apparent, exposure of the image precursor composition is achieved by a different wavelength, that is different from that used to activate the photoinhibitor. Generally the image precur- sor composition is activated by longer wavelength energy than will activate the photoinhibitor.
  • the exposure of the image precursor composition is achieved through the use of heat or light or both together.
  • light is used or is present in a thermal exposure, it is of a wavelength or an intensity that does not activate the photoinhibitor.
  • the light exposure used to imagewise activate the photoinhibitor to inhibit image formation can include energy of wavelengths and intensities that are incapable of activating the image precursor composition in preference to the photoinhibitor, as shown, in examples hereinafter described.
  • filters may be used, particularly for broad-band exposures.
  • thermal energy is used to expose the image precursor composition, it is generated in a total absence of light, such as by a hot block, hot stylus, or heated rollers in a dark room.
  • photoinhibitor means a single compound or a mixture of compounds which respond to activating radiation having a wavelength greater than 300 nm, to inhibit the release of ligands by the cobalt(lll) complex.
  • the photoinhibitor can comprise one or more compounds which themselves have a sensitivity that responds to wavelengths longer than 300 nm, or it can comprise a compound whose sensitivity responds only to wavelengths shorter than 300 nm, and a spectral sensitizer which increases the native sensitivity to beyond 300 nm.
  • An imaging element containing the radiation-sensitive composition of the invention can comprise one or more operatively associated layers, with the image precursor composition being contained in one or more of the layers. That is, the image-forming material of the image precursor composition can either be admixed with the photoinhibitor, or it can be in a separate, adjacent layer where it responds to the ligands which are released by the cobalt(III) complex, as is more fully described hereafter.
  • the photoinhibitor and the image precursor composition are in chemical association, that is, are either admixed together in a single layer, or are in contiguous layers either as manufactured or as processed.
  • This composition includes at least 1) a cobalt(III) complex containing releasable ligands and 2) an image-forming material cabaple of generating an image upon release of said ligands. If the cobalt(lll) complex is thermally stable, i.e., it will not release ligands in response to an exposure which is primarily thermal in nature, then one or more destabilizer materials preferably is included, as defined and described hereafter.
  • an amplifier can also be included in the image precursor composition.
  • an "amplifier" is a reducing .agent precursor composition or compound which interacts with the image precursor composition to generate additional initiators of the imaging reaction, whereby an internal gain, usually expressed as enhanced density, is achieved compared to that which results without the amplifier.
  • the initiators so generated are amines, and a highly useful example of an amplifier for generating such additional amine initiators is o-phthalaldehyde. The reason for such preference is that o-phthalaldehyde also functions as an image-forming material, as is hereinafter described.
  • the amplifiers can be compounds which chelate with the cobalt(II) produced from cobalt(III).
  • Such chelating compounds contain conjugated ⁇ -bonding systems capable of forming with such cobalt(II), additional reducing agents for remaining cobalt(III) complexes.
  • Typical amplifiers of this class, and necessary restrictions concerning pKa values of the anions that can be used in the cobalt(III) complex in such circumstances, are described in Research Disclosure, Volume 135, July 1975, Publication No. 13505.
  • any cobalt(III) complex containing releasable ligands and which is thermally stable at room temperature will function in this invention, whether or not it is thermally stable within the processing temperatures used.
  • Such complexes on occasion have been described as being “inert”. See, e.g., U.S. Patent No. 3,862,842, Columns 5 and 6.
  • the ability of such complexes to remain stable, i.e., retain their original ligands when stored by themselves or in a neutral solution at room temperature until a chemically or thermally initiated reduction to cobalt(II) takes place is so well known that the term "inert" will not be applied herein.
  • Such cobalt(lll) complexes feature a molecule having a cobalt atom or ion surrounded by a group of atoms, ions or other molecules which are generically referred to as ligands.
  • the cobalt atom or ion in the center of these complexes is a Lewis acid while the ligands are Lewis bases.
  • cobalt is capable of forming complexes in both its divalent and trivalent forms
  • trivalent cobalt complexes i.e., cobalt(III) complexes, are employed in the practice of this invention, since the ligands are relatively tenaciously held in these complexes, and released when the cobalt is reduced to the (11) state.
  • Preferred cobalt(III) complexes useful in the practice of this invention are those having a coordination number of 6.
  • a wide variety of ligands can be used with cobalt(III) to form a cobalt(III) complex. The one of choice will depend upon whether the image-forming material described hereinafter relies upon amines to generate a dye or the destruction of dye, or upon the chelation of cobalt(II) to form a dye image. In the latter case, amine ligands or non-amine ligands can be used, whereas in the former case amine ligands are preferred as the source of initiators for the image-forming reaction.
  • Useful amine ligands include, e.g., methylamine, ethylamine, ammines, and amino acids such as glycine nato.
  • ammine refers to ammonia specifically, when functioning as a ligand, whereas "amine” is used to indicate the broader class noted above.
  • highly useful with all the embodiments of the image precursor composition hereinafter described are the ammine complexes.
  • the other amine complexes achieve best results when used with particular destabilizer materials hereinafter described, for example, photoreductants.
  • cobalt(III) complexes useful in the practice of this invention can be neutral compounds which are entirely free of either anions or cations.
  • anion refers to non-ligand anions, unless otherwise stated.
  • the cobalt(III) complexes can also include one or more cations and anions as determined by the charge neutralization rule. Useful cations are those which produce readily soluble cobalt(lll) complexes, such as alkali metals and quaternary ammonium cations.
  • anions can be used, and the choice depends in part on whether or not an amplifier is used which requires that the element be free of anions of acids having pKa values greater than about 3.5. Otherwise, the choice of anions is significant only to the extent that it determines whether or not the complex is thermally stable when heated to the temperature at which the composition or element is processed.
  • thermally unstable means that the complex decomposes at the temperature in question sufficiently to release enough ligands to start the intended reaction of the image precursor composition, as described herein. If a thermally unstable complex is used with the image-forming material alone as the image precursor composition, the complex is preferably unstable only at temperatures greater than 100°C. If a thermally stable complex is to be used a destabilizer material must be included, the complex is preferably stable up to a temperature of at least 130°C.
  • the anions which tend to render the complex thermally unstable include those that decompose readily to a radical, such as trichloroacetate; those forming unstable heavy metal salts, such as azido; and those which are themselves reducing agents, such as 2,5-dihydroxy-benzoate; N,N-dimethyldithiocarbamate; and 1-phenyl-tetrazolyl-5-thiolate.
  • a radical such as trichloroacetate
  • unstable heavy metal salts such as azido
  • those which are themselves reducing agents such as 2,5-dihydroxy-benzoate; N,N-dimethyldithiocarbamate; and 1-phenyl-tetrazolyl-5-thiolate.
  • any anion can be selected if an anion is necessary for charge neutralization, provided the anion is compatible.
  • anions are considered “compatible” if they do not spontaneously cause a reduction of cobalt(III) complex at room temperature. As noted, a complex does not require anions if it is already neutral.
  • the image-forming material of the image precursor composition can comprise compounds or compositions in addition to the cobalt(III) complex and destabilizer material, if any, or it can be the same compound as is used as a destabilizer material. It can be a dye-forming material, or a dye which is bleachable. Examples of dye-forming materials which also comprise destabilizer materials used to interact with the cobalt(III) complex, as discussed hereinafter, include 4-methoxynaphthol, which forms a blue dye when oxidized, and protonated diamine destabilizer material which when associated with a conventional color coupler will form a dye when it is oxidized by the reduction of the cobalt(III) complex.
  • image-forming materials used in addition to a destabilizer material include o-phthalaldehyde, also used as an amplifier; an ammonia-bleachable or color-alterable dye (cyanine dyes, styryl dyes; rhodamine dyes, azo dyes, and pyrylium dyes); a dye-precursor such as ninhydrin; or a diazo-coupler system. Details of these examples are set forth in Research Disclosure, Volume 126, October 1974, Publication No. 12617, Part III, noted above. Still another alternative is to admix with the cobalt(III) complex, chelating compounds which will react with cobalt(II) to form a dye image.
  • o-phthalaldehyde also used as an amplifier
  • an ammonia-bleachable or color-alterable dye cyanine dyes, styryl dyes; rhodamine dyes, azo dyes, and pyrylium dyes
  • Ammonia-bleachable materials will, of course, produce an imagewise absence of dye in the exposed areas.
  • ammonia-bleachable materials and color-alterable materials when incorporated into an element, preferably are used in a separate adjacent layer that is associated with the photoinhibitor layer after the latter is exposed.
  • the image precursor composition includes destabilizer materials in those instances wherein the cobalt(III) complex is thermally stable.
  • destabilizer materials are those which render the otherwise thermally stable cobalt(III) complex susceptible to release of the ligands when appropriately exposed.
  • the exact mechanism by which these destabilizer materials cause the release of the ligands from the cobalt complex is not understood in most instances, other than that such release does occur and cobalt(II) is produced, except where inhibited by the photoinhibitor photoproducts. Because the mechanism of these destabilizer materials is largely uncertain, the subclasses under which various examples fall are uncertain and not necessarily mutually exclusive.
  • the destabilizer materials must be compatible with the cobalt(III) complex. Usually, this is not a problem, "compatible destabilizer materials” being used here to mean materials that do not interfere with the complex, such as by precipitating it or by spontaneously reducing it.
  • destabilizer materials useful with the complex include organo-metallics such as ferrocene and 1,1-dimethyiferrocene, and tricarbonyls such as N,N-dimethylaniline chromium tricarbonyl, as well as organic materials, and may or may not require an amplifier such as phthalaldehyde.
  • destabilizer materials comprising 4-phenyl catechol and quinone photoreductants, hereinafter described, do not require the use of an amplifier compound.
  • Other destabilizer materials will not release the ligands, when appropriately exposed, in amounts sufficient to generate observable dye in the same or an adjacent layer without the presence of,an amplifier such as o-phthalaldehyde.
  • o-phthalaldehyde comprises part of the image precursor composition, for preferred results, whether or not it actually is required to produce observable results.
  • o-phthalaldehyde in an image precursor composition appears to involve, in the preferred embodiments, the formation with ammonia of an adduct which is a reducing agent (see structure A in equation 1 below).
  • the adduct itself causes reduction of remaining cobalt(lll) complex and releases more ligands. Such release produces an internal gain.
  • the initial NH 3 comes from the cobalt(lll) complex on exposure, either because-of its own thermal instability, or because of activation by a destabilizer material, by one of several mechanisms described hereafter.
  • o-Phthalaldehyde also forms a dye imaging material, oligomer (B), in addition to its amplifying function as a reducing agent precursor for cobalt(lll). Further explanation can be found in DoMinh et al, "Reactions of Phthalaldehyde with Ammonia and Amines", J. Org. Chem. Vol. 42, Dec. 23, 1977, p. 4217.
  • Useful destabilizer materials are the following thermally responsive organic materials and equivalents thereof:
  • Ar is arylene including substituted arylene, such as phenylene and naphthylene, wherein the substituents, if any, are electron withdrawing groups such as nitro, sulfoalkyl containing from 1 to 5 carbon atoms, halogen such as chloride, fluoride and the like, and substituted alkyl such as trihalosubstituted methyl; and
  • R 16 represents a hydrogen atom or an alkyl group having from 1 to 3 carbon atoms.
  • destabilizers induce the release of the ligands from the cobalt(lll) complex in the presence of heat. As noted, they may or may not require the presence of an amplifier-dye former such as phthalaldehyde. Some of them, such as destabilizer materials (a) through (d), are quite clearly reducing agents per se. Some like destabilizer material (k) are heat-responsive reducing agent precursors. Some, such as destabilizer material (e) and others are heat-responsive amine precursors. They are particularly useful with amine-responsive reducing agents and reducing agent precursors such as phthalaldehyde that form reducing agents in the presence of amines.
  • destabilizer materials (h), (i) and (j) are believed to be base precursors which form a base in the presence of heat.
  • Destabilizer materials (a) through (d) which are direct reducing agents do not require the presence of an amplifier such as o-phthalaldehyde, although an amplifier is effective to increase the speed of an element or composition of the invention which incorporates these compounds.
  • Quinone photoreductants are yet another class of destabilizer materials which are useful in inducing the release of amines from the cobalt complex.
  • the quinones which are particularly useful as photoreductants include ortho- and para-benzoquinones and ortho- and para-naphthoquinones, phenanthrenequinones and anthraquinones.
  • the quinones may be unsubstituted or incorporate any substituent or combination of substituents that does not interfere with the conversion of the quinone to the corresponding reducing agent.
  • substituents include, but are not limited to, primary, secondary and tertiary alkyl, alkenyl and alkynyl, aryI,' alkoxy, aryloxy, alkoxyalkyl, acyloxyalkyl, aryloxyalkyl, aroyloxyalkyl, aryloxyalkoxy, alkylcarbonyl, carboxy, primary and secondary amino, aminoalkyl, amidoalkyl, anilino, piperidino, pyrrolidino, morpholino, nitro, halide and other similar substituents.
  • Aryl substituents are preferably phenyl substituents.
  • Alkyl, alkenyl and alkynyl substituents, whether present as sole substituents or in combination with other atoms, typically contain 20 or fewer (preferably 6 or fewer) carbon atoms.
  • a preferred class of photoreductants are internal hydrogen source quinones; that is, quinones incorporating labile hydrogen atoms. These quinones are more easily photo-reduced than quinones which do not incorporate labile hydrogen atoms.
  • Particularly preferred internal hydrogen source quinones are 5,8-dihydro-1,4-naphthoquinones having at least one hydrogen atom in each of the 5- and 8-ring positions.
  • Other preferred incorporated hydrogen source quinones are those which have a hydrogen atom bonded to a carbon atom to which is also bonded the oxygen atom of an oxy substituent or a nitrogen atom of an amine substituent with the further provision that the carbon-to-hydrogen bond is the third or fourth bond removed from at least one quinone carbonyl doubled bond.
  • the term "amine substituent" is inclusive of amide and imine substituents.
  • photoreductants do not require the use of an amplifier, but such a use gives improved results.
  • the quinone photoreductants rely upon a light exposure between 300 nm and about 700 nm to form the reducing agent which reduces the cobalt(lll) complex. It is to be noted that thermal irradiation is not needed, after the light exposure, to cause the redox reaction to take place. However, an additional thermal exposure can be used to drive the reaction to completion. Furthermore, heat is desirable to insure the formation of dye B described above.
  • the activity of some of the above described destabilizers, particularly those that respond to thermal radiation, can be enhanced by the addition of a dodecanamide.
  • Photoinhibitors which are sensitive to radiation longer than 300 nm are selected because the plastic film supports for the imaging elements and the optical glass in the exposing system absorb radiation shorter than 300 nm. However, photoinhibitors which are sensitive only to radiation shorter than 300 nm are useful in conjunction with spectral sensitizers.
  • Such UV-sensitive photoinhibitors include carbon tetrabromide, 2-tribromomethyl sulfonylbenzothiazole, 2-bromo-2-tosylacetamide, 2,2-dibromo-2-phenyl-sulfonylacetamide, A-tribromoethanol and 2-bromo-2-nitro-1,3-trimethyiene glycol dibenzoate.
  • Useful spectral sensitizers include rhodamine, carbocyanine and cyanine dyes, Eosin and Erythrosin, triphenylmethane dyes, thiazine dyes, anthroquinonoid and styryl dyes. Specific examples of such sensitizers are disclosed in Yamada et al U.S. Patent No. 3,503,745.
  • Preferred embodiments are those in which the photoinhibitor comprises a composition free of accompanying spectral sensitizers.
  • Highly useful examples of such photoinhibitors are photolytic acid generators, although it is not known whether all photolytic acid generators will function as photoinhibitors.
  • 0-nitrobenzaidehyde is a known photolytic acid generator which is not useful because it complexes with cobalt, and is therefore incompatible in the composition of the invention. Therefore, only those photolytic acid generators are useful which are capable of inhibiting the release of amines without interfering with the desired reaction in some other way.
  • any photoinhibitor having the desired property of inhibiting the release of amines in response to an exposure can be utilized.
  • the mixture of image precursor composition and photoinhibitor is intended to be used as a dry coating composition, it is preferable that the photoinhibitor be capable of being coated without extensive volatilization.
  • a photoinhibitor is to be used with a photo- reductant, each of the two photoresponsive compounds are selected so that their wavelengths of maximum absorption do not overlap appreciably.
  • photoinhibitor compounds are photolytic acid generators having an inherent sensitivity to radiation of a wavelength longer than about 300 nm., including the following materials as well as equivalents thereof:
  • an imaging element comprises a support coated with a single layer containing an image precursor composition and a photoinhibitor as described above.
  • the image precursor composition and the photoinhibitor can be in one or more layers.
  • the outermost layer can be coated on a separate support and disposed in reactable association subsequently, such as after exposure of the photoinhibitor composition.
  • the image-forming material can be included either as an integral portion of the element of the invention, or it can be subsequently associated therewith as a separate image-recording layer.
  • the image-forming material in those embodiments wherein the image-forming material is an integral part of the element, it can either be admixed with the image precursor (cobalt(lll) complex) preferably as a dye-forming material, or it can be in a separate, adjacent layer. In those embodiments wherein it is admixed with the cobalt(III) complex, it is highly preferred that the image-forming material is also an amplifier, such as o-phthalaldehyde which also functions as a reducing agent precursor.
  • the image-forming material is also an amplifier, such as o-phthalaldehyde which also functions as a reducing agent precursor.
  • Yet another alternative is to imbibe the photoinhibitor into the image precursor composition, such as by spraying or otherwise applying a solution of the photoinhibitor to the element already containing the precursor composition.
  • the image precursor composition and photoinhibitor are contained in a layer or layers coated onto a support.
  • Any conventional photographic support can be used in the practice of this invention.
  • Typical supports include transparent supports, such as film supports and glass supports, as well as opaque supports, such as metal and photographic paper supports.
  • the support can be either rigid or flexible.
  • the most common photographic supports for most applications are paper and transparent film supports.
  • Suitable exemplary supports are disclosed in Product Licensing Index, Volume 92, December 1971, Publication No. 9232, at page 108, and Research Disclosure, Volume 134, June 1975, Publication No. 13455, published by Industrial Opportunities Limited, Homewell, Havant, Hampshire P09 1 EF, United Kingdom.
  • the support can incorporate one or more subbing layers for the purpose of altering its surface properties so as to enhance the adhesion of the radiation-sensitive coating to the support.
  • the image-precursor composition can include a binder.
  • a binder Any binder compatible with cobalt(lll) complexes can be used, for example, the binders listed in the aforesaid Publication No. 12617 of Research Disclosure, especially paragraph I(D). Typical of such binders are acetates, cellulose compounds, vinyl polymers, polyacrylates and polyesters. In those embodiments relying upon o-phthalaldehyde as the image-forming material and/or as an amplifier, it is preferred that the binder be selected which will maximize the minimum neutral densities produced during exposure and development.
  • binders include certain polysulfonamides, for example, poly(ethylene-co-1,4-cyclohexylenedimethyiene-1-methyl-2,4-benzenesulfonamide) and poly(ethylene-co-hexamethylene-1-methyl-2,4-benzenedisulfonamide), and poly(methacrylonitrile).
  • polysulfonamides for example, poly(ethylene-co-1,4-cyclohexylenedimethyiene-1-methyl-2,4-benzenesulfonamide) and poly(ethylene-co-hexamethylene-1-methyl-2,4-benzenedisulfonamide), and poly(methacrylonitrile).
  • the coating solvent selected will, of course, depend upon the makeup of the composition, including the binder if any.
  • Typical preferred solvents which can be used alone or in combination are lower alkanols, such as methanol, ethanol, isopropanol, t-butanol and the like; ketones, such as methylethyl ketone, acetone and the like; water; ethers, such as tetrahydrofuran, and the like; acetonitrile; dimethyl sulfoxide, dimethylformamide and chlorinated hydrocarbon solvents which are not effective as acid generators, because they volatize out of the coating.
  • the proportions of the non-binder reactants forming the composition to be coated on the imaging element can vary widely, depending upon which materials are being used.
  • a useful range of coating coverage of cobalt(lll) complex is between about 5 and about 50 mg/dm2 .
  • cobalt(III) complex Since a cobalt(III) complex is always present, the molar amounts of other components are expressed per mole of complex.
  • destabilizer materials are incorporated in the composition in addition to cobalt(lll) complex, they can vary widely such as from 0.004 moles of ferrocene to 5 moles of other destabilizers per mole of complex.
  • 5-n-butylbarbituric acid can be present in an amount of between about 0.005 moles and about 5 moles per mole of the complex.
  • the photoinhibitor can be present in an amount from 0.005 to 2.5 moles per mole of cobalt(III) complex.
  • 2,4- bis(trichioromethyt)-6-(p-anisyt)-s-triazine can be present in those amounts.
  • the energy-activatable composition is coated onto the support in a solution by such means as whirler coating, brushing, doctor-blade coating, hopper coating and the like. Thereafter, the solvent is evaporated.
  • exemplary coating procedures are set forth in the Product Licensing Index, Volume 92, December 1971, Publication No. 9232, at page 109, published by Industrial Opportunities Limited, Homewell, Havant, Hampshire P09 1 EF, United Kingdom. Addenda such as coating aids and plasticizers can be incorporated into the coating composition.
  • an overcoat for the energy-activatable layer of the element can provide improved handling characteristics, and can help to retain otherwise volatile components.
  • Useful examples include crosslinked gelatin overcoats crosslinked with a crosslinking agent such as hexamethoxy methyl melamine, and polymers having the recurring units: wherein:
  • the preferred form of the overcoat is a dual coating first of gelatin crosslinked as noted, and as a final coat, a layer of cellulose acetate having an acetyl content of 19 weight percent and an ash content of 0.04 weight percent.
  • element 10 comprises a support 12 and a layer 14 containing, in admixture, an energy-activatable image precursor composition designated by wavy lines, a photoinhibitor, and an image-forming material such as a dye-forming material.
  • the element is exposed through an image 18 to radiation which activates the photoinhibitor, preferably light, designated by arrows 16.
  • the radiation activates the photoinhibitor in portions 20 and 22 of Fig. 1 B to inhibit the image precursor composition, as indicated by the absence of wavy lines, but not in .the unexposed portion 24.
  • Imaging elements containing light-activatable photoreductants are usable even though they also contain light-activatable photoinhibitors because the photoinhibitors are generally activated more rapidly than the photoreductants. Generally the photoinhibitors are activated by shorter wavelength radiation than the photoreductants. Therefore it may be desirable to interpose an optional filter 25, shown in phantom in Fig. 1 A, which transmits shorter wavelength radiation 16 that activates the photoinhibitor but does not transmit longer wavelength radiation that activates the photoreductant.
  • a "Wratten 18A" filter manufactured by Eastman Kodak Company, can be used. "Wratten” is a trade mark.
  • Fig. 1 B the entire element is given a uniform exposure to thermal radiation or light which activates the image precursor composition as indicated by arrows 26.
  • the uniform exposure is to light and it is necessary to prevent the photoinhibitor in portion 24 from responding.
  • a preferred method for accomplishing this is the interposition of a suitable filter 28, shown in phantom in Fig. 1 B.
  • a filter is selected to cut off the light wavelengths which are necessary for the photo-activation of the photoinhibitor, and to transmit the wavelengths, usually longer, useful in activating the photoreductant.
  • a "Wratten 2A" filter can be used.
  • the effect of the uniform exposure of the image precursor composition is to generate a dye in portion 24, Fig. 1 C, and none in the inhibited portions 20 and 22, thus rendering element 10 positive-working.
  • the dye is schematically shown by the superimposed straight lines.
  • the presently preferred embodiment features o-phthalaldehyde as an amplifier and dye-forming material incorporated in layer 14, along with an s-triazine photoinhibitor such as 2,4- bis(trichloromethyl)-6-(p-anisyl)-s-triazine, hexaammine cobalt(lll) trifluoroacetate complex and either 5-butylbarbituric acid or diphenylhydantoin as a destabilizer. lmagewise exposure to light activates the photoinhibitor.
  • an s-triazine photoinhibitor such as 2,4- bis(trichloromethyl)-6-(p-anisyl)-s-triazine, hexaammine cobalt(lll) trifluoroacetate complex and either 5-butylbarbituric acid or diphenylhydantoin as a destabilizer.
  • a subsequent overall thermal exposure such as at 150°C for the barbituric acid and 130°C for the hydantoin, causes reduction of the complex, release of ammonia, formation of the adduct of phthalaldehyde further reduction of remaining cobalt(III) complex, release of more ammonia, and amplified dye formation.
  • the image-forming material of the image precursor composition which can be, for example, o-phthalaldehyde as noted above, can be disposed in an adjacent layer 30, shown in phantom in Figs. 18 and 1 C.
  • layer 30 can be positioned as an overlay in contact with element 10 after the imagewise exposure as shown in Fig. 1 A, or alternatively, it can be overcoated onto layer 14 as an integral portion of element 10.
  • the uniform exposure which activates the image precursor composition, arrows 26, will develop the release of NH 3 ligands in portion 24 only.
  • the NH 3 ligands will migrate to portion 32 of the layer 30 as shown by arrows 34, where either a dye is formed or a preincorporated dye is bleached or altered in color.
  • layer 30 can be removed from or retained on, element 10.
  • Fig. 2A the same element as in Fig. 1A is given a different treatment to render it negative-working.
  • the same identical element, regarJless of the image precursor composition used is rendered negative-working merely by changing the exposure sequence. That is, the process step effectuated by imagewise exposure is now an exposure capable of activating the image precursor composition rather than the photoinhibitor. Parts similar to those previously described bear the same reference numerals to which the distinguishing suffixes "a" are added.
  • the image-forming material of the image precursor composition is a dye-forming material.
  • element 10a comprises the same coating 14a on support 12a as described before.
  • imagewise exposure through image 18a must not activate the photoinhibitor. If exposure 16a is thermal, only the image precursor composition is activated. In such instance, image 18a is selected so as not to significantly reradiate in the "dark" areas. If however, exposure 16a is broadband light radiation, it preferably passes through a suitable filter 28a, shown in phantom, selected to prevent transmission of radiation sufficient to activate the photoinhibitor, but to allow transmission of radiation sufficient to activate the image precursor composition. As noted before, a "Wratten 2A" filter is effective if the photoinhibitor is iodoform and the image precursor composition contains a quinone photoreductant destabilizer. In the case where a photoreductant destabilizer material is used, an optional subsequent thermal exposure can be included. Dye imagewise develops in areas 20a and 22a, Fig. 2B.
  • the element is then given overall exposure arrows 26a of Fig. 2B, to radiation which activates the photoinhibitor to prevent background printup.
  • a suitable filter 25a shown in phantom, to insure that the exposure 26a does not activate the image precursor composition.
  • the negative image can be formed instead in an adjacent layer, not shown, by transfer of ligands thereto from layer 14a.
  • the photoinhibitor includes a compound having a response only to radiation of wavelengths shorter than 300 nm. and a spectral sensitizer, as described above, it is contemplated that the element of the invention is one in which the photoinhibitor and the image precursor composition each occupy two separate but adjacent layers 40 and 50, element 10b of Fig. 3. In this manner, the spectral sensitizer will sensitize only the photoinhibitor and not also the cobalt(III) complex or the destabilizer material, so that photoinitiation of the inhibitor will not also act to activate the image precursor composition.
  • the photoinhibitor layer can optionally include sodium trifluoroacetate, to produce in the presence of the nonvolatile acid generated by the photoinhibitor, trifluoroacetic acid which is sufficiently volatile.
  • Stock solution A was prepared by dissolving 265 mg of the cobalt complex, hexaamminecobalt(I11) trifluoroacetate, 535 mg of o-phthalaldehyde as amplifier and image-former and 30 mg of 2,4- bis(trichloromethyl)-6-p-methoxystyryl-s-triazine as photoinhibitor in 2 g of acetone. To this solution was added 10 g of a 20% solution of the binder poly(ethylene-cohexamethylene-1-methyl-2,4-benzenedisulfonamide) in 1:1 acetone/methylethylketone.
  • Solution B was prepared by dissolving 4 mg of the destabilizer ferrocene (dicyclopentadienyl iron) in 6 g of acetone.
  • Solution C was prepared by dissolving 4 mg of the destabilizer 1,1-dimethyl- ferrocene in 6 g of acetone.
  • Solution D was prepared by dissolving 10 mg of the destabilizer N,N-dimethylaniline chromium tricarbonyl in 6 g of acetone.
  • the exposed film was placed in face-to-face contact with a diazo-coupler recording element as an image forming layer (commercially available from Eastman Kodak Company as Kodak Registered Trade Mark Diazo Type M) and the sandwich was passed twice through a set of rollers heated to 140°C at a speed of 12.7 cm per minute.
  • a positive bluish image of the step tablet was produced with minimum densities of 0.07 and maximum densities of 0.5, when read using red light.
  • the resulting solutions were then coated with a 150-micron doctor blade on subbed poly(ethylene terephthalate) support, dried and then overcoated with a 4.7% aqueous solution of poly(acrylamido-Co-N-vinyl-2 pyrrolidinone-Co-2-acetoacetoxy methacrylate copolymer (50:45:5 by weight) containing 0.05% Surfactant 10G, a nonylphenoxyglycerol coating aid, with a 50-micron doctor blade.
  • Samples of the dried coatings were then exposed for about two seconds through a 0.15 log E step tablet in an IBM Microcopier IID exposing apparatus. Processing for a 7.3 second contact time at 150-155°C in a Canon Kal-Developer Model 360 VC resulted in positive images for each coating.
  • a solution was prepared by dissolving 200 mg of [Co(NH 3 ) 6 ] (CF 3 Co 2 ) 3 , 400 mg of the amplifier and image-former o-phthalaldehyde, and 200 mg of 2,4-bis(trichloromethyl)-6-p-methoxystyryl-s-triazine as photoinhibitor in 2 g of acetone. To this solution were added 8 g of a 20% solution of the binder poly(ethytene-co-hexamethylene-1-methyl-2,4-benzenedisulfonamide) in acetone.
  • the resulting solution was then coated with a 150-micron doctor blade on a subbed poly(ethylene terephthalate) support, and dried.
  • the coating was overcoated with a 5% aqueous solution of the overcoat polymer of Example 1 containing 0.05% Surfactant 10G with a 50-micron doctor blade.
  • a sample of the dried coating was then exposed for about 16 seconds through a 0.15 log E step tablet to the light from a medium pressure mercury arc lamp in an IBM Microcopier IID exposing apparatus and heat processed for a 5.5-second contact time at 150°C in a Canon Kal-Developer, Model 360 VC.
  • a positive image with neutral D-max of about 2.73 and a brownish D-min of 0.21 was obtained.
  • a solution was prepared by dissolving 200 mg of [Co(NH 3 ) 6 ](CF 3 ⁇ CO 2 ) 3 , 400 mg of o-phthalaldehyde (amplifier and image-former), and 200 mg of the photoinhibitor 2,4-bis(trichloromethyl)-6-p-methoxystyryl-s-triazine in 2 g of acetone. To this solution were added 8 g of a 20% solution of the binder poly(ethylene-co-hexamethylene-I-methyl-2,4-benzenedisulfonamide) in acetone.
  • An image precursor composition solution was prepared for Example 10 comprising 400 mg of [Co(NH 3 ) 6 ] (CF 3 ⁇ CO 2 ) 3 , 800 mg of o-phthalaldehyde as amplifier and image-former, 200 mg of N,N-bis(2-hydroxyethyl) dodecanamide as destabilizer enhancer, and 40 mg of 2,4-bis(trichloromethyl)-6-p-methoxystyryl-s-triazine as photoinhibitor in 20 gms of 20% poly(ethylene-co-1,4-cyclohexylenedimethylene-1-methyl-2,4-benzenedisulfonamide (binder) in acetone.
  • Example 10 was repeated except that 4 mg of the destabilizer, 2-carboxycyclohexylamide was used in place of the phthalamic acid. A positive image was produced having D-max/D-min ratio of 2.1/0.06.
  • a solution of an image precursor composition was prepared by dissolving 266 mg of [Co(NH 3 )J (CF 3 ⁇ CO 2 ) 3 and 534 mg o-phthalaldehyde as amplifier and image-former in 2 g of acetone and adding to this 10 g of a 20% solution of the binder, poly(ethylene-co-1,4-cyclohexylenedimethylene-1-methyl-2,4-benzenedisulfonamide) in acetone.
  • Example 12 was repeated except that the photoinhibitor iodoform was replaced with 1 mg of
  • the film was exposed through a silver negative for 7 seconds to a 650-watt incandescent light source (commercially available under the trade name Nashua 120 Multi-Spectrum Copier).
  • a 650-watt incandescent light source commercially available under the trade name Nashua 120 Multi-Spectrum Copier.
  • the dried coating was exposed for 2 seconds through a 0.15 log E step tablet using a Micro Master Diazo T.M. Copier and dye-developed by heating, face up, in a 150°C Canon Kal-Developer, Model 360 VC for 5.5 seconds.
  • a brownish positive image having a D-max of 0.98 and a D-min of 0.17 to blue light was obtained.
  • Example 15 Example 14 was repeated except that the destabilizer material comprised 2-amino-2-thiazoline trichloroacetate.
  • Example 16 was a repetition of Example 14 except the destabilizer material was anilinium trichloroacetate. Both of these produced a satisfactory positive image.
  • the dried coating was exposed for 8 seconds through a 0.15 log E silver step tablet using the Micro Master Diazo T.M. Copier and dye developed by heating, face up, on a 150°C hot block. A neutral positive image having a D-max of 2.56 and D-min of 0.06 was obtained.
  • a solution of an image precursor composition was prepared as follows:
  • Example 18 was 1.2 log E slower and 0.3 higher in neutral D-max than the control which exhibited a D-max of 2.6.
  • Example 18 gave a substantial improvement over the control in processing, or development, latitude.
  • the resulting solution was coated with a 150-micron doctor blade on a subbed poly(ethylene terephthalate) support, dried and then overcoated with a 4.7% solution of the overcoat polymer of Example 1 in water containing 0.05% 10G surfactant coating aid, using a 50-micron doctor blade.
  • the dried coating was then exposed for 2 seconds through a 0.15 log E silver step tablet using a Micro Master Diazo T.M. Copier and dye-developed by heating, face up, on a 160°C hot block. A brownish, positive image having a D-max of 1.30 and D-min of 0.58 to blue light was obtained.
  • Examples 29-31 were the same as Example 28, with approximately the same results, except that the destabilizer materials were:
  • This solution was coated with a 150-micron doctor blade on subbed poly(ethylene terephthalate) support and dried.
  • This image precursor composition layer was then overcoated with a 5% solution of poly(acrylamide-co-N-vinyl-2-pyrrolidone-co-2-acetoacetoxyethylmethacrylate) in water with 0.05% surfactant 10G coating aid using a 50-micron doctor blade and dried.
  • a sample of the film coating was exposed through a silver negative for 8 seconds on an IBM Microcopier IID device and dye-developed by heating in a 155°C Canon Kal-developer, model 360 VC for 5.5 seconds.
  • a black, positive image with a neutral D-min of 0.12 and a D-max of 3.2 was produced.
  • Example 32 was repeated except that the destabilizer material was, respectively, 2-methyl-2-carboxamidothiazolidine, 2-methyl-2-[2-pyridyl]benzothiazoline, and 2-methyl-2-[4-nitrophenyl]-benzothiazoline. When tested at equivalent chemical levels and similar exposure and processing conditions, these materials also yielded satisfactory results.
  • This solution was coated with a 150-micron doctor blade on a subbed poly(ethylene terephthalate) support and dried.
  • This basecoat was then overcoated with a 4.7% solution of the overcoat polymer of Example 1 in water with a 0.05% surfactant 10G coating aid using a 50-micron doctor blade and dried.
  • a sample of the film coating was exposed through a silver negative for 2 seconds on an IBM Microcopier IID device and dye-developed by heating on a 170°C hot block for 10 seconds, support side down.
  • a positive image was produced with a D-min of 0.19 and a D-max of 0.90.
  • Example 36 was repeated except that equivalent amounts of the blocked mercaptotetrazoles listed in Table IV were substituted for that of Example 36.
  • the elements of Examples 37-41 produced comparable results.
  • This film was exposed through a silver negative for 0.5 seconds on an IBM microcopier IID device and dye-developed by heating for 10 seconds face-up-on a 145°C hot block.
  • a stock solution was prepared by adding 798 mg of [Co(NH 3 ) 6 ] (CF 3 .CO 2 ) 3 , 1.6 g of o-phthalaldehyde image-former, and 60 mg of 2,4-bis(trichloromethyl)-6-p-anisyl-s-triazine photoinhibitor to 30 g of 20% solution of poly(ethylene-co-1,4-cyclohexylenedimethylene-1-methyl-2,4-benzenedisulfonamide) in acetone.
  • Example 7 In 1 g of acetone were dissolved 3 mg of 5-n-butylbarbituric acid. 0.1 g of this solution was then added to 1.0 g of the stock solution, coated, overcoated, exposed, and processed as in Example 7 to give a positive image with a D-max of 3.0 and a D-min of 0.1.
  • a quantity of 40 mg of iodoform was dissolved in 1 g of chloroform. To this solution, a quantity of 2 g of the above stock solution was added. The resulting solution was coated with a 100-micron doctor blade on a subbed poly(ethylene terephthalate) support.
  • a sample of this film was exposed for 2 minutes through a silver test object on a U.V. exposing device, available commercially as a Canon Kalfile Printer 340VC. This exposure imagewise generated inhibitor.
  • the film was then given an overall 30-second exposure to tungsten light using a Nashua 120 Multi-Spectrum Copier to photogenerate reductant.
  • the exposed film was placed in face-to-face contact with a diazo recording element (commercially available under the trade name Kodak Diazo Type M) and the sandwich was passed twice at 76.2 cm per minute through a set of rollers heated to a temperature of 100°C.
  • a positive image was developed with a maximum density of 1.0 and a minimum density of 0.07 measured in red light. (The heating step was used to increase the dye-development reaction).
  • This solution was coated with a 100-micron doctor blade on subbed poly(ethylene terephthalate) support and overcoated with a 10% solution of (copolyester 1,1,3-trimethyl-5-carboxy-3-(p-carboxyphenyl)indan bisphenol A) in toluene.
  • a dried coating was exposed to visible light for 0.5 seconds on an IBM Microcopier IID device through a silver negative and a Wratten 2A filter which removes ultraviolet radiation. Upon heating for 15 seconds face-up on a 140°C hot block, a dense black negative image was formed.
  • Example 47 comprised a repetition of Example 46, except that the element was exposed for 6 seconds on an IBM Microcopier IID through a silver negative and a Wratten 34 filter which passes ultraviolet radiation, followed by a 0.5 seconds dye-development exposure through vVratten 2A filter. Fifteen seconds of heating face-up on a 140°C hot block developed a dense positive image.

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Claims (16)

1. Procédé de formation d'image consistant
- à réaliser une première exposition à un rayonnement qui active un composé photoinitiateur ou un mélange de tels composés, comme décrit ultérieurement, d'un produit formateur d'image contenant, dans une ou plusieurs couches adjacentes, (a) une composition constituant un précurseur d'image, activable par une énergie, comprenant au moins un complexe de cobalt III ayant des ligands libérables, (b) une substance formatrice d'image qui crée une image en réponse à la libération des ligands, ce précurseur d'image activable par une énergie étant une composition activable par toute énergie électromagnétique dans les plages où elle n'est pas inhibée par un photoinitiateur déjà exposé, comme décrit ultérieurement, cette composition, lorsqu'elle est-activée par une exposition à une énergie électromagnétique, foumissant une image par formation d'une densité ou bien par destruction ou modification d'une densité préexistante et (c) comme photoinitiateur, un composé unique ou un mélange de composés qui ne forme pas un complex avec le cobalt et qui est sensible à un rayonnement activateur ayant une longueur d'onde supérieure à 300 nm et qui inhibe la libération des ligands du complexe de cobalt III ou qui inhibe l'action des ligands libérés sur la substance formatrice d'image lors d'une exposition à un rayonnement activateur d'une longueur d'onde différente de celle qui active la composition précurseur d'image,
et ensuite à exposer le produit formateur d'image à un rayonnement d'une longeur d'onde qui active le précurseur d'image activable par une énergie.
2. Procédé conforme à la revendication 1, dans lequel la couche de la substance formatrice d'image est adjacente à la couche de la composition constituant le précurseur d'image activable par une énergie sur un seul support.
3. Procédé conforme à la revendication 2, dans lequel la composition constituant le précurseur d'image est activée par un chauffage uniforme.
4. Produit formateur d'image contenant, dans une ou plusieurs couches adjacentes, (a) une composition constituant un précurseur d'image, activable par une énergie, comprenant au moins un complexe de cobalt III ayant des ligands libérables, (b) une substance formatrice d'image qui crée une image en réponse à la libération des ligands, ce précurseur d'image activable par une énergie étant une composition activable par toute énergie électromagnétique dans les plages où elle n'est pas inhibée par un photoinitiateur déjà exposé, comme décrit ultérieurement, et cette composition, lorsqu'elle est activée par une exposition à une énergie électromagnétique, fournissant une image par formation d'une densité ou bien par destruction ou modification d'une densité préexistante, et (c) comme photoinitiateur, un composé unique ou un mélange de composés qui ne forme pas une complexe avec le cobalt et qui est sensible à un rayonnement activateur ayant une longueur d'onde supérieure à 300 nm et qui inhibe la libération des ligands du complexe de cobalt III ou qui inhibe l'action des ligands libérés sur la substance formatrice d'image lors d'une exposition à un rayonnement activateur d'une longueur d'onde différente de celle qui active la composition formant précurseur d'image.
5. Produit formateur d'image conforme à la revendication 4, dans lequel le photoinhibiteur est un composé hétérocyclique ayant au moins un groupe substituant trihalogénométhyle.
6. Produit formateur d'image conforme à la revendication 5, dans lequel le photoinhibiteur est un composé hétérocyclique de formule:
Figure imgb0052
où E représente un atome d'hydrogène, un groupe méthyle ou trihalogénométhyle,
R21 représente un atome d'hydrogène ou un groupe alkoxy ayant jusqu'à 5 atomes de carbone,
R22 représente un atome d'hydrogène, un atome d'halogène, un groupe nitro ou bien un groupe alkyle, dialkylamino ou alkoxy dans lequel le radical alkyle a jusqu'à 5 atomes de carbone,
R23 représente un atome d'hydrogène ou un groupe alkoxy ayant au plus 5 atomes de carbone ou bien, associé à R24, R23 représente les atomes non métalliques nécessaires pour compléter un noyau aromatique,
R24 représente un atome d'hydrogène ou bien associé à R23, R24 représente les atomes non métalliques nécessaires pour compléter un noyau aromatique,
Z7 représente les atomes non métalliques nécessaires pour compléter un ou plusieurs hétérocycles contenant de 6 à 10 atomes,
m" est égal à 0, 1 ou 2,
X" représente un atome d'halogène.
7. Produit formateur d'image conforme à la revendication 5, dans lequel le photoinhibiteur est la 2,4-bis (trichloromethyl)-6-(p-anisyl)-s-triazine, la 2,4-bis (trichlorométhyl)-6-(4-méthoxystyryl)-s-triazine, la 2,4-bis(trichlorométhyl)-6-[4-(4-diméthylaminophényl)-1,3-butadiényl]-s-triazine, la 2-tri- bromométhylquinoléine, la 2-tribromométhylquinoxaline, le 2-tribromomethyl-4-oxo-4H-1-benzo- pyrane, la 2,4-bis(trichtorométhyt)-6-<1-naphtyf)-s-triazine, la 2,4-bis(trichlorométhyl)-6-(4-méthoxy-1-naphtyl)-s-triazine, le tribromométhylbenzène ou la 2,3-bis(tribromométhyl)quinoxaline.
8. Produit formateur d'image conforme à la revendication 4, dans lequel le photoinhibiteur a la formule:
Figure imgb0053
où R25 représente un groupe alkyle ayant au plus 3 atomes de carbone, un groupe aralkyle ayant 7 ou 8 atomes de carbone, ou bien, associé à R26, R25 représente les atomes nécessaires pour compléter un hétérocycle condensé,
R26 représente un atome d'halogène ou bien, associé à R25, R26 représente les atomes nécessaires pour compléter un hétérocycle condensé,
R27 représente un atome d'hydrogène ou un groupe alkoxy ayant au plus 3 atomes de carbone,
X"' représente un atome d'halogène,
9. Produit formateur d'image conforme à la revendication 8, dans lequel le photoinhibiteur est le N-méthyl-o-nitrotrifluoroacétanilide, le N-benzyl-o-nitrotrifluoroacétanilide, le N-benzyl-2-nitro-5-méthoxytrifluoro-acétanilide ou la 6-bromo-8-nitro-N-trifluoroacétylbenzo [b] pipéridine.
10. Produit formateur d'image conforme à la revendication 4, dans lequel le photoinhibiteur a la formule:
Figure imgb0054
où R17 représente un atome d'hydrogène, un groupe phényle ou un groupe alkyle ayant au plus 4 atomes de carbone,
R18 représente un groupe alkyle ayant au plus 4 atomes de carbone ou bien un groupe adamantyle,
R19 représente un atome d'hydrogène ou d'halogène,
Z6 représente
Figure imgb0055
R20 représente un atome d'hydrogène ou un groupe alkyle, ayant au plus 5 atomes de carbone,
X' représente un anion.
11. Produit formateur d'image conforme à la revendication 4, dans lequel le photoinhibiteur est le p-toluènesulphonate de N-méthyl-3-diazo-4-quinolinium, le perchlorate de N-méthyl-3-phényl-2,1-benzisoxazolium ou le fluoroborate de N-méthyl-3-phényl-2,1-benzisoxazolium.
12. Produit formateur d'image conforme à la revendication 4, dans lequel le photoinhibiteur est un des composés organiques halogénés iodoforme, tétrabromure de carbone, β-tribromoéthanol, hexa- bromoéthane, tribromoacétate d'éthyle, tribromoacétamide, tribromométhyl benzène, .pentabromo- éthane, α,α,α,-tribromoacétophénone ou 3-nitro-α,α,α,-tribromoacétophénone.
13. Produit formateur d'image conforme à l'une quelconque des revendications précédentes dans lequel le complexe de cobalt III est instable et se décompose à une température supérieure à 100°C en quantité suffisante pour libérer assez de ligands pour amorcer la réaction de la composition constituant un précurseur d'image.
14. Produit formateur d'image conforme à l'une quelconque des revendications 4 à 12 dans lequel le complexe de cobalt III est thermiquement stable jusqu'à une température d'au moins 130°C et dans lequel la composition constituant un precurseur d'image contient un composé destabilisant qui rend le complexe de cobalt III, autrement stable thermiquement, susceptible de libérer des ligands quand il est exposé d'une manière appropriée, mais qui n'interfère pas avec le complexe de cobalt III.
15. Produit formateur d'image, conforme à l'une quelconque des revendications précédentes, dans lequel la composition constituant un précurseur d'image contient un amplificateur qui est une composition ou un composé précurseur d'agent réducteur qui réagit avec la composition constituant un précurseur d'image pour créer des initiateurs supplémentaires de la réaction de formation d'image, ce que fournit un gain interne, habituellement exprimé sous forme d'une densité accrue, comparé à celui obtenu sans amplificateur.
16. Produit formateur d'image conforme à la revendication 15, dans lequel l'amplificateur est l'o-phtalaldéhyde.
EP19780300914 1977-12-28 1978-12-28 Méthode pour l'obtention d'une image et élément pour la formation d'une image par inhibition à base de complexes de cobalt (III) Expired EP0003263B1 (fr)

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CA1144412A (fr) * 1978-12-20 1983-04-12 Anthony Adin Element qui renferme une couche de colorant a base de o-dialdehyde aromatique, une composition de visualisation photosensible, et une couche surimposee de polymere
US4247625A (en) * 1978-12-20 1981-01-27 Eastman Kodak Company Imaging processes, elements and compositions featuring dye-retaining binders for reaction products of cobalt complexes and aromatic dialdehyde
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US4469773A (en) * 1983-06-15 1984-09-04 Eastman Kodak Company Carbamoyloxy substituted couplers in a photothermographic element and process
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US10351661B2 (en) 2015-12-10 2019-07-16 Ppg Industries Ohio, Inc. Method for producing an aminimide

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CA1116915A (fr) 1982-01-26
GB2012445B (en) 1982-07-14
JPS54500062A (fr) 1979-11-15
GB2012445A (en) 1979-07-25
EP0003263A1 (fr) 1979-08-08
WO1979000448A1 (fr) 1979-07-26

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