EP0100126B1 - Procédé pour l'enregistrement du rayonnement électromagnétique - Google Patents

Procédé pour l'enregistrement du rayonnement électromagnétique Download PDF

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Publication number
EP0100126B1
EP0100126B1 EP83201076A EP83201076A EP0100126B1 EP 0100126 B1 EP0100126 B1 EP 0100126B1 EP 83201076 A EP83201076 A EP 83201076A EP 83201076 A EP83201076 A EP 83201076A EP 0100126 B1 EP0100126 B1 EP 0100126B1
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Prior art keywords
film
tellurium
layer
imaging
reductant precursor
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German (de)
English (en)
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EP0100126A2 (fr
EP0100126A3 (en
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Terry Ta-Jen Yu
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Energy Conversion Devices Inc
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Energy Conversion Devices Inc
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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
    • G03C1/72—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705
    • G03C1/73—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705 containing organic compounds
    • G03C1/734—Tellurium or selenium compounds

Definitions

  • the invention relates to an improved method for recording electromagnetic radiation in which a fixed image is provided.
  • imaging materials used are, in certain cases, particular organic compounds.
  • Some of these heretofore known methods employ mixtures of inorganic compounds such as silver halide with one or more particular types of organic compounds as sensitizers.
  • the invention relates to a method whereby electromagnetic radiation is impinged upon a photosensitive film to produce a change in at least one photosensitive layer thereof, and the layer is developed by heat.
  • the layer comprises a reducible image-forming compound, a reductant precursor which will abstract labile hydrogen from a labile hydrogen source under the influence of imaging energy to become a reducing agent with respect to the image-forming compound, a source of labile hydrogen for reaction with said reductant precursor, and a matrix in which said image-forming compound, reductant precursor, and source of labile hydrogen are combined to form a composition which may be applied to a substrate.
  • the film is prepared by combining the ingredients, i.e. the tellurium derivative, the reductant precursor, source of labile hydrogen and additional ingredients in a suitable matrix to form an emulsion which may be spread on a film on an appropriate carrier or substrate.
  • a latent image in the film is formed by exposure to imaging energy, for example a light image.
  • a visible image is developed, such as by heating the exposed film as described in United States Patent No. 4,142,896.
  • the film is desirably fixed to avoid darkening or other undesirable modification of the film resulting from exposure to light or the passage of time.
  • United States Patent No. 4,142,896 also describes a method of fixing the tellurium imaging film by removing the sensitizer and inactivating unreacted imaging ortho-tellurium material.
  • the film is fixed by contacting the film with a chloroform/toluene (20:80 by volume) solution saturated with ammonia or with organic amines.
  • this fixing is relatively slow, generally taking about thirty minutes.
  • fixing method requires the use of relatively toxic and hazardous compounds.
  • the use of chloroform/toluene is unsuitable for several types of desirable matrix polymers, such as the CAB type, because the chloroform/toluene mixture dissolves such polymers.
  • Another type of fixing method is possible in which the film is fixed by contacting the film with an alcohol, such as isopropanol, for example.
  • an alcohol such as isopropanol
  • a small amount of ketone such as acetone, for example, may also be included with the alcohol.
  • ketone such as acetone
  • methods and dry process imaging films which utilize a reductant precursor and a reducible imaging compound are provided which are self-fixing.
  • a separate fixing step or fixing chemicals are not required and a fixed film is provided as a result of normal developing conditions, such as heating at 150 ⁇ 155°C for 30-90 seconds, for example.
  • heating at 150 ⁇ 155°C for 30-90 seconds for example.
  • self-fixing dry process imaging films can be made by controlling the amount of reductant precursor present in the film.
  • the amount of reductant precursor present in the film is present in a limited amount such that under normal developing conditions, essentially all of the reductant precursor is extracted by heat development of the film.
  • the time of normal development is five minutes or less.
  • the film is such that substantially all of the reductant precursor is removed from the film after less than two minutes of development at 150°C. It is the unreacted reductant precursor (i.e. that which is not changed to a reducing agent as a result of exposure to imaging energy) that must be removed.
  • the type of reductant precursor utilized should be heat-extractable when combined with the other film components in a matrix.
  • the film-forming composition comprising an image-forming compound and a reductant precursor, contains a proper amount of reductant precursor so that when film made from the film-forming composition is developed by heat, essentially all of the reductant precursor is removed.
  • "essentially all of the reductant precursor” means that a sufficient amount such that the amount remaining does not cause the film to be significantly altered by the passage of time or exposure to light.
  • the film-forming compositions may contain other components, as discussed.
  • the amount of reductant precursor present in the film-forming composition is variable. Generally, sufficient reductant precursor is present such that film made from the composition produces the desired change in optical density to allow formation of an image.
  • the specific amount of reductant precursor will be dependent upon the type of reductant precursor and the other components present in the film-forming composition. However, the amount of reductant precursor should not be so great as to be present in the film after normal development in amounts which cause the film to darken significantly or produce significant undesirable modification of the film as a result of exposure to light or the passage of time.
  • the amount of reductant precursor can be as desired, and preferably is that amount for a particular composition which provides the desired film speed and optical density. The optimum amount of a particular reductant precursor for a particular formulation can easily be determined simply by formulating film-forming compositions containing various amounts of reductant precursor and testing the performance of the films made therefrom.
  • the object of the invention is to provide a method for recording electromagnetic radiation.
  • the method includes impinging the radiation upon a photosensitive film to produce a change in at least one property thereof.
  • the film is made from a photosensitive composition which includes an image-forming tellurium compound and a reductant precursor which will abstract labile hydrogen from a labile hydrogen source under the influences of imaging energy to become a reducing agent with respect to the image-forming tellurium compound.
  • the composition also includes a source of labile hydrogen for reaction with the reductant precursor and a matrix in which the tellurium compound, reductant precursor and source of labile hydrogen are combined in amounts effective to form a composition which may be applied to a substrate.
  • the composition is characterized by - said reductant precursor being present in an amount in the range of 0,5% by weight of the total layer and developing by heat said layer for a period of time sufficient to develop and fix the layer by removing essentially all of the reductant precursor.
  • An emulsion formulated in accordance with the present invention contains a tellurium compound, a reductant precursor and an appropriate matrix.
  • other components may also be included in the emulsion.
  • a diol may be included, preferably a glyceryl compound of U.S. Patent No. 4,281,058.
  • a masked reducing agent or water may be included in the emulsion.
  • a base may also be included, preferably when a masked reducing agent is included.
  • an alcohol may also be included, preferably when a glyceryl compound of U.S. Patent No. 4,281,058 is included.
  • reducible organo-metallic imaging compounds and other reducible metal compounds, other than tellurium compounds may be utilized in accordance with the invention.
  • other metals which can form organo-metallic imaging compounds include copper, silver, nickel, mercury and cobalt.
  • cobalt imaging compounds are disclosed in U.S. Patent No. 4,201,588 to Adin et al.
  • Specific organo-metallic compounds which may be used include, for example, copper-2,4-pentanedionate, nickel-2,4-pentanedionate, mercury acetate and silver behenate.
  • the image-forming tellurium A number of image-forming tellurium compounds are described in the prior art and such compounds are generally useful in the present invention. In general, the present invention contemplates using these and other tellurium compounds which undergo analogous reduction reactions in the presence of a reductant precursor as hereinafter described.
  • the image-forming tellurium compound is of the type that requires the presence of a reducing agent, such as a reducing agent formed from a reductant precursor upon exposure to imaging energy, to form a significant image.
  • a reducing agent such as a reducing agent formed from a reductant precursor upon exposure to imaging energy
  • tellurium compounds possess certain properties which adapt them especially for use in imaging processes. In general, these are compounds from which, as a result of the imaging and developing steps generally referred to above, elemental tellurium is deposited from the tellurium compounds.
  • Tellurium is chain-forming in character, and it is generally deposited from the tellurium compounds useful for photographic purposes (preferably including thin needles), the compounds being capable of rapid nucleation and growth as crystallites, which crystallites grow as chains and largely or mainly as needles.
  • Such chains or needles are opaque and are characterized by excellent light scattering properties to produce good optical density observed after thermal or other development.
  • Effects which may involve oxide formation are substantially restricted to surface effects as distinguished from effects which cause degradation through the bodies of the needles or chains.
  • the tellurium imaging compound is an organo-tellurium compound such as disclosed in U.S. Patent No. 4,142,896 of Chang et al.
  • organo-tellurium compounds such as disclosed in U.S. Patent No. 4,142,896 of Chang et al.
  • These compounds are organic tellurium compounds which inherently possess sensitizer properties (and/or may be mixed with a separate sensitizer) in which the tellurium is linked directly to at least one carbon atom or the organic radical of the organo-tellurium material, the organic tellurium compound being of one structure and having a detectable characteristic which is capable of undergoing a change in response to the application of imaging energy in the form of particle or wave radiation to produce a material of different structure having another detectable characteristic.
  • the material having a different structure and different detectable characteristics resulting from the imaging step is sometimes referred to as the "image-forming compound".
  • the tellurium imaging compound may be an organo-metallic compound such as disclosed in U.S. Patent No. 4,062,685.
  • a particularly advantageous subgroup of the imaging organo-tellurium compounds utilized in the practice of the present invention comprises organic compounds which contain an organo radical and halogen attached directly to the tellurium atom, there being at least one carbonyl group in the organo radical. Certain of them are adducts of tellurium halides, notably tellurium tetrachloride, with organic compounds, notably ketones or similar chromophores, containing at least one carbonyl group in the organic compound. They may, thus, be considered or characterized as organo-tellurium compounds or adducts containing halogen, namely, chlorine, bromine, iodine, and fluorine, attached directly to the tellurium atom.
  • organo-tellurium compounds namely, chlorine, bromine, iodine, and fluorine
  • imaging compounds having two carbonyl-containing organo radicals.
  • Those which are especially useful in the practice of the present invention have chlorine as the halogen but, in certain cases, although generally less satisfactory, other halogens can be present.
  • the imaging compounds should be selected to be soluble or homogeneously dispersible in any particular matrix material which may be utilized, as is described hereafter.
  • x is 2 or 3.
  • organo-tellurium imaging compounds which contain a trihalide group, as, for instance, acetophenone tellurium trichloride, tend to have relatively low melting points (about 70 ⁇ 80°C), and are more hygroscopic and less stable than those generally similar compounds containing two halogen atoms and, therefore, such trihalides are less desirable for use in the practice of the present invention.
  • acetophenone tellurium trichloride tend to have relatively low melting points (about 70 ⁇ 80°C), and are more hygroscopic and less stable than those generally similar compounds containing two halogen atoms and, therefore, such trihalides are less desirable for use in the practice of the present invention.
  • a more limited class of this particular sub-group of imaging organo-tellurium compounds may be represented by the formula where Ar is an aromatic hydrocarbon radical, which may be substituted or unsubstituted, as indicated above, and Hal is halogen, especially chlorine.
  • Ar is an aromatic hydrocarbon radical, which may be substituted or unsubstituted, as indicated above, and Hal is halogen, especially chlorine.
  • Hal is halogen, especially chlorine.
  • This subgroup of compounds, particularly where Hal is chlorine, represents especially advantageous embodiments of the invention, with respect to the imaging orano-tellurium compounds which are used in the practice of the present invention.
  • Another subgroup of imaging organo-tellurium compounds, useful in the practice of and contemplated by the present invention, which do not contain a carbonyl group in an organo radical but in which tellurium is linked directly to carbon are compounds which may be considered or characterized as tellurium tetrahalide adducts of ethylenic or of acetylenic hydrocarbons. These compounds are generally conveniently produced by reacting 1 to 2 moles, particularly 2 moles, of the ethylenic or acetylenic hydrocarbon with 1 mole of tellurium tetrahalide, especially preferred for such use being TeCI 4 .
  • Illustrative of the ethylenic and acetylenic hydrocarbons which can be adducted with tellurium tetrahalides to produce such imaging organo-tellurium compounds are propylene; butene-1; isobutylene; butene-2, 2,3-dimethyl-2-butene; 3,3-dimethyl-1-butene; 2,4-dimethyl-1-pentene; 4,4-dimethyl-1-pentene; 2,5-dimethyl-3-hexene; dipentene; 1,1-diphenylethylene; 1-heptene, 1-hexene; 2-methyl-1-hexene; 3-methyl-1-hexene; 4-methyl-1-hexene; 2-ethyl-1-hexene; 2-isopropyl-1-hexene; 2-methyl-1-pentene; 2-methyl-2-pentene; 2-ethyl-2-pentene; 3-methyl-1-pentene; piperylene; vinylcyclohex
  • tetrahalides of tellurium in which the halide is at least one member selected from the group consisting of chlorine and bromine are also useful as the image-forming material in the present invention.
  • Such tellurium halides are fully described in U.S. Patent No. 4,066,460.
  • Typical tellurium tetrahalides which may be used are TeCl 41 TeCl 2 Br z ; and TeCIBr 3 . TeC1 4 is especially useful.
  • Still another group of image-forming compounds are certain compounds derived from tellurium tetrahalides which are described in U.S. Patent 4,106,939 to Chang et al. These involved compounds are adducts of tellurium tetrahalide with aromatic amines exemplified by the tellurium tetrachloride adduct of dimethylaniline, which adduct is free of diazo groups. More specifically, these tellurium tetrahalide adducts are formed by combining a tellurium tetrahalide with an aromatic amine in which nitrogen attached directly or indirectly to the aromatic radical is substituted by alkyls containing from 1 to 4 carbon atoms, the imaging organo-tellurium material being free from diazo groups.
  • the active tellurium compounds may, if desired, be formed in situ, for example, by using bis (acetophenone) tellurium dichloride or a tellurium oxide or a tellurium salt in combination with a suitable organic compound. Sometimes, the in situ formation is promoted by the presence of an acid. For example, tellurium oxide or alkali metal tellurates may be combined with one of the glycols described below to form a tellurium-organic compound complex which is active. It is believed that the reaction is analogous to the reaction between organic tellurium compounds such as described above and a diol. Preliminary information suggests that the reaction is favored by an acidic medium. Small amounts of an acid such as anhydrous hydrogen chloride may be added. Alternatively, halogen-containing tellurium compounds will provide the requisite acidity.
  • the reductant precursor In addition to the tellurium image-forming compound, the imaging systems of the present invention include a reductant precursor, or sensitizer, which, as described above, is a compound that, under the influence of activating energy, has the property of extracting labile hydrogen from a hydrogen donor to become a reducing agent with respect to the image-forming tellurium compound. The activated reducing agent then reduces the tellurium compound to produce the desired image.
  • the hydrogen donor may be an external source of hydrogen such as an alcohol specifically provided for the purpose. However, the hydrogen donor may equally well be an appropriate group which is a part of the molecular structure of the reductant precursor.
  • Preferred reductant precursors useful in the present invention are quinones, particularly 2-isopropoxynapthoquinone; 9,10-phenanthenequinone; and 2-t-butyianthraquinone.
  • Other specific reductant precursors include: 3-chloro-2-isopropoxy-1, 4-naphthoquinone; 3-chloro-2-isopropoxy-1,4- anthraquinone; 3-chloro-2-isopropoxy-6,7-diphenyl-1,4-naphthoquinone; 3-chloro-2-(3'-Pentoxy)-1,4-naphthoquinone; 3-chloro-2-(2'-butoxy)-1,4-naphthoquinone; 3-chloro-2-(3',3'-dimethyl-2'-butoxy)-1,4-naphthoquinone; 2,3-diisopropoxy-1,4-naphthoquino
  • Especially useful reductant precursors from the aforementioned group include 3-chloro-2-isopropoxy-1,4-naphthoquinone, 3-chloro-2-isopropoxy-1,4-anthraquinone and 2,3-diisopropoxy-1,4-naphthoquinone. These reductant precursors exhibit good sensitivity to electromagnetic radiation in the visible range, while allowing the film to have good speed.
  • Benzophenone although not a quinone, is also useful as a reductant precursor, as are a number of the simpler ketones.
  • a factor of importance in the selection of reductant precursors is the spectral range to which the reductant precursors respond. For that reason, the simple ketones are not generally useful for recording visible light since their spectral sensitivity is in the far ultraviolet region.
  • reductant precursors which are sensitive in the range of up to about 400 nm and, therefore, are useful only in the ultraviolet range: Benzophenone; acetophenone; 1,5-diphenyl-1,3,5-pentanetrione; ninhydrin; 4,4'-dibromobenzophenone; and 1,8-dichloroanthraquinone.
  • reductant precursors can be utilized, particularly those of the type of substituted or unsubstituted polynuclear quinones, of which class some have been mentioned above, and others of which are 1,2-benzanthraquinone; 2-methylanthraquinone; 1-chloroanthraquinone; 7,8,9,10-tetrahydro- naphthacenequinone; 9,10-anthraquinone; and 1,4-dimethylanthraquinone.
  • reductant precursors will be effective or equally effective, with each given imaging material, even taking into account the utilization of imaging energy in the sensitivity range of the reductant precursor employed and that suitable selections of combinations of particular imaging materials and particular reductant precursors will be required to be made for achieving desirable or optimum results. Further, various reductant precursors will require different amounts of heating during development in order to remove substantially all of the reductant precursor from the film. Such selections, however, can be made relatively readily.
  • reductant precursors have ⁇ n * states, both singlet and triplet, of lower energies than n, n * states and, at least in most cases, compounds which have their n, n * states of lowest energy will not be photosensitively effective, although, in certain limited cases, compounds which fulfill the test of having lower energy ⁇ ⁇ n * than ⁇ ⁇ n * transitions do not function as reductant precursors.
  • the above consideration is, in the main, an effective one for determining in advance whether a given compound will function as a reductant precursor for use in the practice of the present invention.
  • a simple preliminary empirical test in any given instance can readily be carried out if necessary by preparing a test emulsion using the desired imaging compound and reductant precursor.
  • a masked reducing agent may be included.
  • a typical masked reducing agent thus is the compound 1-phenyl-2-benzoylamido-3-pyrazolidinone:
  • a more complete description of masked reducing agents may be found in Belgian Patent 863,052 of July 19, 1978, and reference thereto is made for additional descriptions thereof.
  • a new class of masked reducing agents may be substituted, represented by the general formulae wherein Y is hydrogen or said compound containinq at least one group.
  • R 1 may be alkyl, alkanoyl, alkoxycarbonyl, phenyl, benzyl, benzoyl, nitrophenyl, benzylcarbonyl, phenylmethyl, phenylethyl or phenylpropylcarbonyl or aminocarbonyl.
  • R 2 , R 3 and R 4 each, and independently, may be hydrogen, alkyl or phenyl and amino.
  • R 4 may be phenyl, nitrophenyl, halophenyl, alkyl, mono-, di- or trihaloalkyl, benzoyl, alkylphenyl, or alkylcyanophenyl.
  • the masking group may be substituted at either one or both of the amino hydrogen sites of the reducing agent.
  • the alkyl groups referred to above may contain up to seven carbon atoms. Such compounds are conveniently accessible through reaction of the parent hydrazine or pyrazoline with an isocyanate of the formula
  • a base can be included.
  • the inclusion of a base provides the unexpected result of improving the speed (light sensitivity) and/or improving the optical density of the exposed portions after development of imaging film made with such compositions.
  • the inclusion of a base may also reduce the background fog or optical density of unexposed portions of the film.
  • the compositions may contain other components, as discussed.
  • the base may be organic or inorganic and should be sufficiently alkaline to ionize the masked reducing agent.
  • any base which improves the performance of the film such as, for example, increased speed, increased optical density of exposed portions or decreased fog of unexposed portions, can be utilized.
  • bases which produce unwanted deleterious effects will be avoided.
  • Suitable inorganic bases include, for example, metal hydroxides and ammonium hydroxide. More specifically, alkali metal hydroxides and alkaline earth metal hydroxides can be utilized.
  • Useful alkali metal hydroxides include those of lithium, sodium, potassium, rubidium and cesium. Lithium hydroxide is the preferred alkali metal hydroxide.
  • Useful alkaline earth metal hydroxides include those of magnesium, calcium and barium. The hydrated form of the metal hydroxide can be used. It is anticipated that more than one base can be included in the imaging film composition.
  • the organic base may be an aliphatic amine compound or a nitrogen atom containing heterocyclic compound.
  • Suitable amines for use in accordance with the invention include primary, secondary and tertiary amines which may be aliphatic or aromatic. More particularly, suitable amines are those such as, for example, methylamine, di-methylamine, trimethylamine, ethylamine, diethylamine, triethylamine, n-, di-n-and tri-n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tertbutylamine, and n-tetradecylamine. In general, those amines of the following formula may be suitable: where R is aliphatic (for example CH 3 , C 2 H s , C 3 H 7 , etc.).
  • the R radical may be unsubstituted or substituted by various organic or inorganic radicals, which do not interfere with the desired imaging effect.
  • Cyclic compounds such as pyridine and piperidine, are also suitable, and may be unsubstituted or substituted by various organic or inorganic radicals, which do not interfere with the desired imaging effect.
  • the base ionizes the masked reducing agent facilitating the formation of a complex between the ionized masked reducing agent, positive tellurium ions and the latent image formed by the reductant precursor after exposure of the film to imaging energy.
  • the complex is believed to be very susceptible to electron transfer, facilitating formation of a visible image.
  • alkaline earth or alkali metal hydroxides are preferred over organic bases.
  • the metal ions from the base may form a beneficial complex with the reductant precursor which makes the reductant precursor more active.
  • the amount of base present in the film-forming composition is variable. Generally, there is no minimum amount of base required to provide an improved film. However, the degree of improvement is related to the amount of base present, up to a certain amount, for each particular film formulation and base. Beyond that amount, generally the photoresponse of the film diminishes.
  • the optimum amount of a particular base for a particular formulation can easily be determined simply by formulating film-forming compositions containing various amounts of a particular base and testing the performance of the films made therefrom.
  • the Dio/ there may also be included a diol which reacts with the tellurium compound to form an active intermediate complex. While the chemistry of the complex is not well understood, we believe that, in general, the complex requires approximately 2 moles of diol for each mole of tellurium. Preferably, the diol, when present, is used in excess of the minimum amount to form a complex since the diol will also function as a source of labile hydrogen to provide the source of hydrogen required in the reaction of the reductant precursor.
  • the present invention can be practiced without the inclusion of a diol, the presence of a diol is preferred especially when a masked reducing agent is present.
  • the presence of a diol serves to markedly reduce the optical density of unexposed areas (i.e., thus increasing the contrast between the exposed and unexposed areas).
  • masked reducing agents can be used in the absence of a diol, tellurium film compositions containing masked reducing agents tend to have a relatively high optical density in the unexposed areas because the reducing capacity of the masked reducing agent is not fully inhibited by the masking group.
  • the following table illustrates a number of diols which may be used:
  • the diol is of a more complex type than disclosed in the above-mentioned Belgian patent application.
  • These more complex diols are the subject matter of U.S. Patent No. 4,281,058.
  • R12 may be alkyl, acyl, thiazolinyl, alkenyl, phenyl, alkylphenyl, alkenylphenyl, hydroxyalkylphenyl, benzyl, alkylbenzyl, alkoxybenzyl, hydroxyalkylbenzyl, or halobenzyl and similar radicals.
  • Preferred compounds of the foregoing structure are those in which the radical R12 is benzyl or a substituted benzyl.
  • the use of the diols of the foregoing structure has been found to be preferred since they are more effective in reducing the optical density of the unexposed areas than are the diols described in Belgian Patent 854,193.
  • Ancillary Ingredients In addition to the foregoing principal ingredients of the present formulation, ancillary ingredients may be included for various purposes. Thus, for example, it has been found that certain materials enhance the shelf life of unexposed virgin dry film compositions of the present invention, and in certain instances, they also enhance the sensitivity of said film compositions.
  • Illustrative embodiments of such additional or supplemental materials which contain ether or polyether linkages in the molecules thereof, are such materials or polymers as polyethylene-20 sorbitan monolaurate; polyethylene-20 sorbitan monooleate; Polyox-10; Polyox-80; Polyox-750; polyethylene glycol-400 distearate; polyethylene glycol-600 distearate; poly (1,3-dioxolane); poly (tetrahydrofuran); poly (1,3-dioxepane); poly (1,3-dioxane); polyacetaldehydes; polyoxymethylenes; fatty acid esters of polyoxymethylenes; poly (cyclohexane methylene oxide); poly (4-methyl-1,3-dioxane); polyoxetanes; polyphenylene oxides; poly [3,3-bis (halomethyl) oxocyclobutane]; poly (oxypropylene) glycol epoxy resins; and copolymers of
  • Such materials can be incorporated in the imaging film compositions in varying amounts, generally from 5 to 20% by weight of the solid imaging film compositions. In certain cases they enhance or prolong the shelf life or storage life, under given storage conditions, as much as 50% or even very substantially more timewise, and, as indicated, they also, in various cases, effectively increase film sensitivity.
  • the inclusion in the imaging films of reducing sugars has been found, generally speaking, to bring about an enhancement in density of the image area (O.D. image - O.D. background), when the film is imaged as disclosed above and then developed, for instance, at about 120-150 0 C and for the order of about 15 seconds, especially where the imaging film is freshly prepared or not older than about a day after initial preparation.
  • Such films when exposed to imaging energy and then developed resulted in the production of a positive image (i.e., the optical density is greater in the nonexposed areas than in the exposed areas) in contrast to the negative working system which exists in the usual practice of the present invention.
  • reducing sugars in the imaging compositions also enables development of the image, after exposure to imaging energy, to take place at lower temperatures, even at room temperatures, in a period of several hours, for instance, commonly in 10, 12 or 15 hours.
  • the reducing sugars which can be employed are many, illustrative of which are dextrose, glucose, arabinose, erythrose, fructose, galactose, fucose, mannose and ribose. Especially effective are dextrose, arabinose, galactose, fucose and ribose.
  • the reducing sugars can be used in variable amounts, but generally in equivalent amounts, or somewhat smaller or greater, in relation to the amount of imaging organo-tellurium materials in the imaging compositions.
  • ancillary ingredients may be utilized, which can have the effect of increasing the sensitivity of the film and/or optical density after exposure.
  • a film composition in accordance with the present invention is completed by dissolving the ingredients and optional ingredients described above in a suitable matrix.
  • the matrix should be as concentrated as is practicable in the active ingredients, i.e., the least amount of matrix is preferably used.
  • the amount of matrix should be sufficient as to just retain the various active ingredients in a solid solution.
  • An additional quantity of matrix may be used, however, that obviously tends to dilute the concentration of active ingredients, thereby slowing down the photo-response of the film composition.
  • the selection of matrix materials must be related to the active ingredients used so as to provide the maximum solubility for any particular composition.
  • the matrix materials into which the imaging organo-tellurium materials, and the separate sensitizers when employed, are incorporated to produce the imaging film or coating, are solids at room temperature, and they can be selected from a relatively large number of materials. Care should be taken to insure that the matrix material does not absorb undesired components, such as excess water from the atmosphere. They should desirably be at least in part of amorphous character and it is especially desirable that they be glassy, polar amorphous materials having a glass transition temperature, which desirably should not exceed about 200°C and may be as low as 50°C, and, better still, should be within the range of 80 ⁇ 120°C. They are generally polymeric materials.
  • cyanoethylated starches celluloses and amyloses having a degree of substitution of cyanoethylation of ? 2; polyvinylbenzophenone; polyvinylidene chloride; polyethylene terephthalate ("MYLAR"); cellulose esters and ethers such as cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, acetyl cellulose, methyl cellulose, ethyl cellulose, hydroxypropyl cellulose, polyvinylcarbazole; polyvinyl chloride; polyvinyl methyl ketone; polyvinyl alcohol; polyvinylpyrrolidone; polyvinyl methyl ether; copolymers of vinylidene chloride and acrylonitrile; polyvinyl acetate, polyvinyl butyral; polystyrene; polymethyl methacrylate; polyvinyl pyrrolidone; sty
  • polyvinyl formal 15/95% which is a white, free flowing powder having a molecular weight in the range of 24,000-40,000 and a formal content expressed as percent polyvinyl formal of approximately 82%, possessing high thermal stability, excellent mechanical durability, and resistance to such materials as aliphatic hydrocarbons, and mineral, animal and vegetable oils.
  • These polymeric materials or resins and their preparation are well known to the art.
  • various grades of cellulose acetate butyrate polymers sold by the Eastman Kodak Company under the trade designation "CAB", particularly "CAB 500­5".
  • the imaging organo-tellurium materials, sensitizers and any other ingredients which may be incorporated into the imaging film or coating or layer and their functioning as dry or essentially dry film-forming materials to provide thin films and providing mechanical durability in the finished imaged film, at least many of them appear also to play a chemical or physical role in the imaging process by providing, importantly, a source of readily easily abstractable hydrogen and, thus, appear to play a significant role in the latent image formation mechanism, as discussed hereafter.
  • it may be desirable to decrease the viscosity of the matrix which can be done, by way of illustration, by the addition of certain plasticizers, for instance, dibutylphthalate or diphenylphthalate, which additions tend to result in the production of images desirably of higher optical densities but which, however, also tend to have the disadvantage of increasing background fogging.
  • plasticizers for instance, dibutylphthalate or diphenylphthalate
  • matrix materials of the type which contain basic groups may complex with the imaging organo-tellurium materials and, therefore, to the extent that such complexing may occur, the use of such matrix materials should be avoided.
  • compositions of the invention may include an alcohol.
  • the alcohol will be utilized when a diol as previously described is present in the composition.
  • the alcohol and diol may form a complex with the tellurium compound, providing a film having enhanced speed and/or improved background fog.
  • the alcohol may be primary, secondary or tertiary. Primary monohydric alcohols are preferred, such as n-butanol and n-propanol, for example.
  • the composition may also include water.
  • Formulation of Fi/m Compositions In the production of the films or thin layers of the imaging material compositions, which are generally prepared in the form of solutions or homogeneous dispersions and coated or laid down on a substrate, it is especially desirable to dissolve or homogeneously disperse the ingredients in an organic solvent.
  • suitable solvents are methyl ethyl ketone (MEK), dimethylformamide (DMF), chloroform, tetrahydrofuran (THF), dimethylacetamide (DMA), dioxane, dichloromethane and ethylene dichloride, or compatible mixtures of such organic solvents or with other organic solvents.
  • a particularly useful solvent is a 50:50 mixture of dichloromethane and methyl ethyl ketone.
  • the finished films or coatings prior to exposure to imaging energy, contain a small percentage, commonly of the general order of 2 to 3%, by weight of the film or coating, or organic solvent, for instance, dimethylformamide (DMF) since its presence appears to play a favourable role in the sensitivity of the system in relation to the latent image formation and/or ultimate image obtained after the development step.
  • DMF dimethylformamide
  • the imaging film or coating thickness are variable but will usually fall within the range of about 1 to about 35 pm with about 5 to 15 pm generally being a good average.
  • the thickness of the coating is about 20 pm.
  • increases in the coating thickness make removal of the reductant precursor as a result of heat development more difficult.
  • the production of the imaging organo-tellurium materials, and the coating, handling and processing operations, to the extent which may be required, are carried out under appropriate light conditions, as those skilled in the art will readily understand.
  • the formulation of the coating compositions and the coating and drying operations are conveniently carried out under amberlite filtered light (weak transmission at 550 nm).
  • the dry film prior to imaging is desirably stored in the dark.
  • avoidance of contact of certain of the ingredients with certain metals may be in order where undesired reactions, such as reductions, may occur.
  • the vessels or containers, stirrers, etc., utilized should be made of glass or other vitreous materials or other materials inert to the coating ingredients to insure against contamination or possible undesired reactions.
  • the proportions of the matrix, the imaging organo-tellurium material and the reductant precursor are variable.
  • the matrix material which is a normally solid material, that is, solid at room temperature, will be employed in amounts in excess of any one of the other materials and will also usually be present in major amount, that is more than 50% and broadly in the range up to 90% by weight, of the total materials present in the imaging composition.
  • the imaging organo-tellurium material generally also a normally solid material, will ordinarily constitute from 1 to above 20 parts per 100 parts of matrix, usually 5-10 parts per 100 parts of matrix.
  • the reductant precursor where it is a separate ingredient, which is usually a solid, will usually be employed in lesser proportions, commonly of the order of about 0.5 to 3%, usually 0.8 to 2.0%, by weight, of the imaging composition.
  • the area density of the reductant precursor is desirably selected so that up to about 70-95% of the photons falling on the film in the region of the absorption bands of the reductant precursor are absorbed.
  • concentrations of reductant precursor would leave the dark side of the film unexposed and no advantage would thus be served.
  • the mole concentration of the imaging organo-tellurium material to that of the reductant precursor should be about 5:2.
  • the concentration of the polymer matrix material should be sufficient to produce an essentially amorphous film without bringing about precipitation of the imaging organo-tellurium material, the sensitizer and other supplemental ingredients when utilized. Excess polymer matrix material also tends to decrease the sensitivity of the film.
  • the amount of diol should be present in a concentration sufficient to provide at least 2 moles of diol for each mole of tellurium compound, and preferably to provide up to a ratio of 6:1 moles.
  • a complex is formed between the diol and the tellurium compound in a molar ratio of 2: 1, and that excess diol above that is useful to provide a source of labile hydrogen for reaction with the reductant precursor.
  • Larger amounts of the diol may be used if desired. To some extent, improved results are obtained when these larger amounts of diol are used; however, there is a point of diminishing returns above which increasing the amount of diol will not provide commensurate improvement in photoresponse of the finished film.
  • the masked reducing agent may be present in amounts of 1 % up to 200% by weight of the tellurium compounds.
  • Measurably improved sensitivity can be found in accordance with the present invention with even very small amounts of masked reducing agent and within limitations the degree of improvement is in proportion to the amount of masked reducing agent which is incorporated in the film. Again, however, a law of diminishing returns is observed, and while large amounts of the masked reducing agent will be incorporated, on the order of 2 to 4 times the amount of tellurium compound, beyond these large amounts the increase in photo-response obtained is not commensurate with the increased amount of masked reducing agent incorporated.
  • the film-forming compositions as described above will be applied to any suitable substrate.
  • Glass, porcelain, paper and various plastic substrates have been found suitable.
  • transparency is obviously desirable.
  • film of polyethylene terephthalate have been found particularly suitable.
  • Other substrates include, for example, polyimides, nylon and triacetyl cellulose.
  • a tellurium imaging film in accordance with the invention was made and tested. 0.625 grams of bis(acetophenone) tellurium dichloride, 0.15 grams of isopropoxy-1,4-naphthoquinone (IPNQ), 0.625 grams of masked 1-phenyl-3-pyrazolidone of the formula: 2.4 grams of ortho-methoxy benzyl glyceryl ether, 10.42 grams of CAB-500-5, 3.0 milliliters of n-butanol and 160 milliliters of a 50:50 mixture (by volume) of methylene dichloride and methyl ethyl ketone were stirred together in complete darkness at room temperature until a homogeneous viscous solution was obtained. The solution was then coated on a polyester substrate at a thickness of 20 pm and the resulting film heated in an oven at 50°C for three hours.
  • the film was tested by exposing the film to imaging energy through a photographic step tablet having eleven steps and an optical density range of approximately 0.3 to 3.05. The step tablet was in contact with the film during exposure.
  • a Honeywell Strobonar Model No. 710 Xenon flash tube was utilized to provide imaging energy, spaced approximately 228.6 cm (nine inches) from the film.
  • the film was developed by heating the film at a temperature of 150°C for either 45 or 90 seconds.
  • the developed film was tested to determine how well the film was fixed by placing a frame of the film in a Bell & Howell Model SR-VIII microfilm reader for one or more hours in the viewing position.
  • the minimum and maximum optical density (OD) of the film was thereafter measured with a MacBeth Model T-P 504 Densitometer using a red filter. The following results were obtained:
  • Example 2 The same procedure set forth in Example 1 was utilized to make and test film made as in Example 1 except that 0.190 grams of 3-chloro-1-isopropoxy-1,4-naphthoquinone (CIPNQ) was utilized in place of IPNQ. The following results were obtained:
  • Example 2 The same procedure set forth in Example 1 was utilized to make and test film made as in Example 1 except that in place of IPNQ, 0.315 grams of 2,3-diisopropoxy-1,4-naphthoquinone was utilized. The following results were obtained:
  • Example 2 The same procedure set forth in Example was utilized to test film made as in example 1, from the following composition: 0.625 grams of bis(acetophenone) tellurium dichloride, 0.15 grams of isopropoxy-1,4-naphthoquinone (IPNQ), 0.625 grams of masked 1-phenyl-3-pyrazolidone of the formula: 2.4 grams of ortho-methoxy benzyl glyceryl ether, 10.42 grams of CAB-500-5,3.0 milliliters of n-butanol, 0.3 grams of 2-phenylidone-1,3-dione (PID), 4 milligrams of pinacyanol chloride (QB), 3 milligrams of lithium hydroxide (LiOH ⁇ H 2 O), 3 milligrams of indophenol blue (IPB) and 160 milliliters of a 50:50 mixture (by volume) of methylene dichloride and methyl ethyl ketone. The following results were obtained:
  • Example 2 The same procedure set forth in Example 1 was utilized to make and test the film of Example 4 except that in place of IPNQ, 0.190 grams of CIPNQ was utilized. The following results were obtained:
  • Example 2 The same procedure set forth in Example 1 was utilized to make and test the film of Example 4 except that in place of IPNQ, 0.315 grams of DIPNQ were utilized. The following results were obtained:

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Claims (9)

1. Une méthode pour enregistrer une radiation électromagnétique dans laquelle on a prévu une image fixe, laquelle méthode comprend le contact de ladite radiation avec un film photosensible pour produire un changement dans au moins une couche photosensible, le développement de ladite couche par chaleur, ladite couche comprend un compose reductible formmant des images, un précurseur de réducteur qui soustraira de l'hydrogène labile à une source d'hydrogène labile sous l'influence d'énergie pourformer des images pour devenir un agent réducteur par rapport au composé formant des images, une source d'hydrogène labile pour réaction avec ledit précurseur de réducteur, ainsi qu'une matrice dans laquelle ledit composé formant des images, ledit précurseur de réducteur et ladite source d'hydrogène labile sont combinés pour former une composition pouvant être appliquée sur un substrat, caractérisér par - ledit précurseur de réducteur étant présent dans une quantité dans l'intervalle de 0.5% en poids de la couche totale et le développement de ladite couche par chaleur pour une période suffisante pour développer et fixer la couche en enlevant essentiellement tout le précurseur de réducteur. 2. La méthode selon la revendication 1, caractérisée par l'épaisseur de la couche se situant entre 1 et 35 micromètres.
3. La méthode selon la revendication 1, caractérisée par l'épaisseur de la couche étant environ 20 micromètres.
4. La méthode selon la revendication 1, caractérisée par un développement à 150―155°C pendant 2 minutes ou moins.
5. La méthode selon la revendication 1, caractérisée par ledit composé formant des images étant un composé organo de cuivre, d'argent, de nickel, de mercure, de cobalt ou de tellure.
6. Une méthode pour enregistrer une radiation électromagnétique dans laquelle on a prévu une image fixe, laquelle méthode comprend le contact de ladite radiation avec un film photosensible pour produire un changement dans au moins une couche photosensible, le développement de ladite couche par chaleur, ladite couche comprend un compose de tellure formant des images, un précurseur de réducteur qui soustraira de l'hydrogène labile à une source d'hydrogène sous l'influence d'énergie pour former des images pour devenir un agent réducteur par rapport au composé le tellure formant des images, une source d'hydrogène labile pour réaction avec ledit précurseur de réducteur, ainsi qu'une matrice dans laquelle ledit composé de tellure, ledit précurseur de réducteur et ladite source d'hydrogène labile sont combinés pour former une composition pouvant être appliquée sur un substrat, caractérisée par - ledit précurseur de réducteur étant présent dans une quantité dans l'intervalle de 0.5% en poids de la couche totale et le développement de ladite couche par chaleur pour une période suffisante pour développer et fixer la couche en enlevant essentiellement tout le précurseur de réducteur.
7. La méthode selon la revendication 6, caractérisée par l'épaisseur de la couche se situant entre 1 et 35 micromètres.
8. La méthode selon la revendication 6 ou 7, caractérisée par l'épaisseur de la couche étant environ 20 micromètres.
9. La méthode selon l'une quelconque des revendications 6-8, caractérisée par un développement à 150―155°C pendant 2 minutes ou moins.
EP83201076A 1982-07-26 1983-07-20 Procédé pour l'enregistrement du rayonnement électromagnétique Expired EP0100126B1 (fr)

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AT83201076T ATE39029T1 (de) 1982-07-26 1983-07-20 Verfahren zur aufzeichnung von elektromagnetischer strahlung.

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CA1246923A (fr) 1988-12-20
AU1698483A (en) 1985-01-24
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JPS5952242A (ja) 1984-03-26
DE3378596D1 (en) 1989-01-05
ATE39029T1 (de) 1988-12-15

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