Combination of photosensitive elements for use in radiography

Abstract

 Combination of photosensitive elements for use in radiography consisting of a pair of radiographic fluores­cent screens and a double-side coated silver halide ra­diographic element. Each screen is arranged adjacent to each silver halide layer and each screen is capable of imagewise emitting radiation to which the adjacent silver halide layer is sensitive when imagewise exposed to X radiation. The combination is characterized in that one fluorescent screen emits a first radiation in a first wavelength region of the electromagnetic spectrum and the other fluorescent screen emits a second radiation in a second wavelength region of the electromagnetic spectrum, and each silver halide layer is substantially insensitive to the radiation emitted by the opposite screen.

Description

FIELD OF THE INVENTION

[0001] The present invention relates to a combination of photosensitive elements for use in radiography and, more in particular, to a combination of a fluorescent phosphor screen pair and a double-side coated silver halide radio­graphic element for use in industrial or medical radiog­raphy.

BACKGROUND OF THE INVENTION

[0002] In radiography, and particularly in medical radiog­raphy, light-sensitive elements having silver halide emulsion layers coated on both faces of a transparent support (called double-side coated silver halide ele­ments) are used. Said double coated silver halide ele­ments are generally used in combination with fluorescent phosphor screens in order to reduce the X radiation expo­sure necessary to obtain the required image. Generally, one fluorescent phosphor screen is used in association with each silver halide emulsion layer of the double coated element. The silver halide emulsions used in the double coated element are sensitized to a region of the electromagnetic spectrum corresponding to the wave length of the light emitted by the phosphor materials used in the fluorescent phosphor screens, thus obtaining a sig­nificant amplification factor.

[0003] The quality of the image obtained upon X radiation exposure of said screen pair and double coated silver halide element combination and development of said double coated silver halide element is negatively affected by crossover exposure. Crossover exposure, which causes a reduction in image sharpness, occurs in double coated silver halide elements when light emitted by one fluores­cent phosphor screen passes through the adjacent silver halide emulsion layer and, the light having been spread by the support, imagewise exposes the silver halide emul­sion layer on the opposite face of the support.

[0004] The crossover exposure causes poor definition even if light-sensitive elements are used which employ reduced silver halide coverages to lower the costs or increase the processing speed of the element. In fact, the de­crease of the emulsion turbidity increases the amount of light available for crossover and therefore worsens the image.

[0005] To reduce the crossover exposure, dyes or pigments can be used within the radiographic element. The absorp­tion of said dyes or pigments is in a region of the elec­tromagnetic spectrum corresponding to the wavelength of the light emitted by the fluorescent phosphor screens. The dyes or pigments absorb some of the light emitted by the fluorescent phosphor screen so that imaging of a sil­ver halide emulsion layer by the opposite screen is re­duced by absorbance of the light from the opposite screen by the anticrossover dyes or pigments. These dyes or pig­ments are eliminated during the photographic developing, fixing and washing process of the exposed material; they can be for instance washed away or, more preferably, bleached while processing the radiographic element.

[0006] The dyes can be incorporated in any layer of the light-sensitive element: in the emulsion layer, in an in­termediate layer between the emulsion and the base, or in the subbing layer of the support base. It is preferred to incorporate the dyes in a layer different from that con­taining the emulsion to avoid possible desensitization phenomena. Since 1978, Minnesota Mining and Manufacturing Company has sold a radiographic element under the name of 3M Trimax^TM Type XUD X-Ray Film to be used in combination with 3M Trimax^TM Intensifying Screens. Such radiographic element comprises a transparent polyester base, each surface of which has a silver halide emulsion layer sen­sitized to the light emitted by the screens. Between the emulsion and the base is a gelatin layer containing water-soluble acid dyes, which dyes can be decolorized during processing and have an absorption in a region of the electromagnetic spectrum corresponding to the wave­length of the light emitted by the screens and of the spectral sensitivity of the emulsion. The dyes are an­chored in the layer by means of a basic mordant consist­ing of polyvinylpyridine.

[0007] In the practical solution of reducing the crossover exposure by using a mordanted dye layer (as described for instance in the European Patent Application 101,295), some problems are created which up to now have not yet been solved properly. In fact, the improvement of image definition involves not only a natural decrease of the light-sensitive element sensitivity caused by the absorp­tion of the transmitted light which otherwise would take part in the formation of a part of the image, but also the possibility of desensitization phenomena due to the migration of dye not firmly mordanted in the silver halide emulsion layer. There is also a problem with re­sidual stain even after processing, the retention of sig­nificant quantities of thiosulfate from the fixing bath which causes image yellowing upon long-time storage on shelf, and lengthening of the drying times after process­ing because of element thickening.

[0008] Other approaches have been suggested to reduce crossover, as reported hereinafter.

[0009] US Patent 3,923,515 discloses a relatively lower speed silver halide emulsion between the support and a higher speed silver halide emulsion layer to reduce crossover.

[0010] US Patent 4,639,411 discloses a photographic ele­ment, to be used with blue emitting intensifying screens,having reduced crossover, said element comprising coated on both sides of a transparent support a blue sen­sitive silver halide emulsion layer and, interposed be­tween the support and the emulsion layer, a blue absorb­ing layer comprising bright yellow silver iodide grains of a specific crystal structure.

[0011] Japanese Patent Application 62-52546 discloses a radiographic element of improved image quality comprising coated on both sides of a transparent support a light sensitive silver halide emulsion layer and, interposed between the support and the emulsion layer, a layer con­taining water insoluble metal salt particles having ad­sorbed on their surface a dye. Said dye has a maximum absorption within the range of ± 20 nm of the maximum absorption of said silver halide and corresponds to the light emitted by intensifying screens. Silver halides are disclosed as preferred metal salt particles.

[0012] Japanese Patent Application 62-99748 discloses a radiographic element of improved image quality comprising coated on both sides of a transparent support a light-­sensitive silver halide emulsion layer and, interposed between the support and the emulsion layer, a silver halide emulsion layer having substantially no light-sen­sitivity.

[0013] The approaches of using light-insensitive silver halide layers as anticrossover layers interposed between the support and the light-sensitive silver halide emul­sion layers, although preferred to using dyes or pig­ments, encounter some problems such as the increase of silver coverage and bad bleaching characteristics in pho­tographic processing (residual stain).

[0014] The following are additional documents illustrating the state of the art.

[0015] BE 757,815 discloses a combination of a silver halide element and an intensifying screen comprising a fluorescent compound emitting light of wavelength less than 410 nm.

[0016] US 4,130,428 discloses a combination of two fluores­cent screens and a double coated silver halide element wherein the maximum emission of the screens is in the wavelength range of 450-570 nm and silver halide layers are sensitive to light in the same wavelength range.

[0017] US 3,795,814, 4,070,583 and GB 2,119,396 disclose rare earth oxyhalide phosphors activated with terbium and/or thulium employed in fluorescent screens having UV emission.

[0018] FR 2,264,306 discloses a combination of a silver halide element and fluorescent screen comprising a rare earth activated rare earth oxyhalide phosphor having it maximum emission in the wavelength range of 400-500 nm.

[0019] EP 88,820 discloses a radiographic fluorescent screen comprising a first blue emitting phosphor layer and a second green emitting phosphor layer to be combined with a silver halide element having spectral sensitivity in the blue-green region ("ortho-type" elements).

[0020] JP 60175-000 discloses a combination of a double coated silver halide element and a screen pair wherein the fluorescent layers of the two screens have different wavelength region emissions and each screen comprises an organic dye to absorb the light emitted by the opposite screen.

[0021] EP 232,888 discloses a combination of a double coat­ed silver halide element and a pair of front and back intensifying screens wherein said front and back screens, emitting light in the same wavelength region, have dif­ferent modulation transfer factors to be used in low en­ergy radiography.

[0022] US 4,480,024 discloses the combination of a silver halide photothermographic element and a rare-earth inten­sifying screen which are uniquely adapted to one another for the purpose of industrial radiographic imaging. The photothermographic element is dye-sensitized to the spec­tral emission of the screen and the combination of screen and element has an amplification factor greater or equal to at least 50. According to this invention preferably a single screen is used in combination with a single-side coated photothermographic element , or double screens with either single-side or a double-side coated photo­thermographic elements, the latter without any signifi­cant benefit and at increased cost of film.

SUMMARY OF THE INVENTION

[0023] The present invention provides a combination of a pair of radiographic fluorescent screens and a double coated silver halide radiographic element. Each screen is arranged adjacent to each silver halide layer and each screen is capable of imagewise emitting radiation to which the adjacent silver halide layer is sensitive when imagewise exposed to X radiation. The combination is characterized in that one fluorescent screen emits a first radiation in a first wavelength region of the elec­tromagnetic spectrum and the other fluorescent screen emits a second radiation in a second wavelength region of the electromagnetic spectrum, and each silver halide lay­er is substantially insensitive to the radiation emitted by the opposite screen.

[0024] In particular, the present invention provides for a combination of a pair of front and back radiographic fluorescent screens and a double coated silver halide radiographic element, wherein the first radiation emitted by said front screen has a wavelength which differs from the second radiation emitted by said back screen by at least 50 nm, and each silver halide layer is substantial­ly insensitive to the radiation emitted by the opposite screen.

[0025] More in particular, the present invention provides for a combination of a pair of front and back radiograph­ic fluorescent screens and a double coated silver halide radiographic element, wherein said front screen comprises a non-actinic radiation, preferably green radiation, emitting phosphor and is arranged adjacent to a front silver halide layer comprising a silver halide emulsion spectrally sensitized to the light emitted by said front screen, and said back screen comprises an actinic radia­tion, preferably UV radiation, emitting phosphor and is arranged adjacent to a back silver halide layer compris­ing a silver halide emulsion insensitized to the visually observable regions of the electromagnetic spectrum.

[0026] The combination of screen pair and double coated silver halide element for use in radiography according to the present invention provides images having superior image quality, particularly less crossover, as compared to conventional radiographic screen pair and double sil­ver halide element combinations without causing negative effects, such as significant loss of sensitivity, residu­al stain, image instability upon storage, excessive ele­ment thickening and increased silver coverage. The combi­nation may be used in industrial or medical radiography.

BRIEF DESCRIPTION OF THE DRAWINGS

[0027] 

Figure 1 is a schematic diagram of a radiographic element and screen pair combination of the present inven­tion.

Figures 2 and 4 are graphs illustrating emission spectra of radiographic fluorescent screens of the present invention.

Figures 3 and 5 are graphs illustrating spectral sensitivity of a double-side coated silver halide radio­graphic element of the present invention.

Figures 6 and 7 are graphs illustrating sharpness and granularity versus sensitivity of radiographic double coated silver halide element and screen pair combina­tions.

DETAILED DESCRIPTION OF THE INVENTION

[0028] The present invention will be now described in de­tail.

[0029] Figure 1 shows in greater detail a combination of the screen pair and the double silver halide element of this invention. The combination comprises three separate photosensitive elements: a double coated silver halide radiographic element 10, a front screen 21 and a back screen 20.

[0030] As shown, the double coated silver halide radio­graphic element 10 comprises a support 11 and coated on its opposite faces are the subbing layers 12 and 13. A front silver halide emulsion layer 15 is coated over the subbing layer 13 and a back silver halide emulsion layer 14 is coated over the subbing layer 12 on the opposite face of the support. Protective layers 16 and 17 are coated over the silver halide emulsion layers 14 and 15, respectively.

[0031] As shown, the front radiographic fluorescent screen 21 comprises a support 29, a reflective layer 27, a fluo­rescent phosphor layer 25 and a protective layer 23. Sim­ilarly, the back radiographic fluorescent screen 20 com­prises a support 28, a reflective layer 26, a fluorescent phosphor layer 24 and a protective layer 22.

[0032] In practical use, the screen pair and the silver halide element are compressed in a radiographic cassette with the front screen arranged adjacent and in close con­tact with the front silver halide emulsion layer and the back screen is arranged adjacent and in close contact with the back silver emulsion halide layer. Imagewise X radiation enters the screen pair and silver halide ele­ment combination through the front screen support 29 and reflective layer 27 and passes the front screen fluores­cent phosphor layer 25. A portion of the X radiation is absorbed in the phosphor layer 25. The remaining X radia­tion passes through the protective layers 23 and 17. A small portion of the X radiation is absorbed in the front silver halide emulsion layer 15, thereby contributing directly to the formation of a latent image in said front silver halide emulsion layer 15. The major portion of the X radiation passes through the subbing layer 13, the sup­port 11 and the subbing layer 12. Again, a small portion of the X radiation is absorbed in the back silver halide emulsion layer 14, thereby contributing directly to the formation of a latent image in said back silver halide emulsion layer 14. Again, the major portion of the X ra­diation passes through the protective layers 16 and 22 and is absorbed in the back fluorescent phosphor layer 24. The imagewise X radiation is principally absorbed in the fluorescent phosphor layers 24 and 25, thereby pro­ducing the emission of longer wavelength radiation. Ac­cording to the present invention, the first radiation emitted by the front fluorescent phosphor layer 25 expos­es the adjacent front silver halide emulsion layer 15, and the second radiation emitted by the back fluorescent phosphor layer 24 exposes the adjacent back silver halide emulsion layer 14. The silver halide emulsions are sub­stantially insensitive to the radiation emitted by the opposite fluorescent phosphor layer. Said radiation emit­ted by a fluorescent phosphor layer passing to at least some extent beyond the adjacent silver halide emulsion layer penetrates the subbing layers and the support to expose the opposite silver halide emulsion layer. This fact, while increasing to some extent the speed of the screen pair and silver halide element combination, would have the effect of impairing the image sharpness by crossover exposure. The terms "actinic" and "non-actinic" radiation according to the present invention are used to indicate, respectively, radiation of wavelenght shorter than 500 nm (Ultraviolet and blue radiation), preferably from 300 to less than 500 nm, and radiation of wavelength from 500 nm upwards (green, red and Infrared radiation), preferably from 500 to 1200 nm. The term "insensitive" as used herein, describes either primary or intrinsic insen­sitivity of the silver halide grain emulsion (or layer including it) to a certain range of wavelengths, as de­fined, or secondary or induced insensitivity (or unreachability) of the silver halide emulsion (or layer including it) in the double silver halide element because of filter action excercised by a further emulsion layer or layers interposed between the considered "insensitive" layer and the radiation emitting screen or by filter dyes or agents included in the considered layer or in such interposed layers. Accordingly, the latent image formed by radiation (preferably comprised between 300 and 1200 nm) exposure in each silver halide emulsion layer is pri­marily formed by exposure to the radiation emitted by the adjacent fluorescent phosphor layer, with no significant contribution by opposite screen. Preferably, the radia­tion exposure necessary to produce a Dmax of 1.0 on said front silver halide layer will produce a Dmax of less than 0.2 on the back silver halide emulsion layer under the same development conditions. Conversely, an exposure at the λ max of the back layer that produces a Dmax of 1.0 will produce a Dmax of less than 0.2 on the front layer.

[0033] The terms "front" and "back" in the present inven­tion are used to distinguish the different elements of the unsymmetrical screen pair and double coated silver halide element combination not their position relating to exposing X radiation source. Accordingly, X radiation may enter the unsymmetrical screen pair and double-side coat­ed silver halide element through either the front fluo­rescent phosphor screen or the back fluorescent phosphor screen.

[0034] The term "silver halide element" in the present in­vention includes both silver halide "photographic" ele­ments which use liquid development to produce the final image and silver halide "photothermographic" elements, often referred to as "dry silver" elements, which do not use liquid development to produce the final image, as described thereinafter. In both photographic and photo­thermographic silver halide elements, exposure of the silver halide to radiation produces small clusters of silver ions. The imagewise distribution of these clusters is known in the art as the latent image. This latent im­age generally is not visible by ordinary means and the light-sensitive element must be further processed in or­der to produce a visual image. This visual image is pro­duced by the catalytic reduction of silver which is in catalytic proximity to the specks of the latent image. The photographic silver halide element is preferably used in medical radiography and the photothermographic silver halide element is preferably used in industrial radiogra­phy.

[0035] Accordingly, the present invention relates to a com­bination of photosensitive elements for use in radiogra­phy comprising two separate front and back X-ray fluores­cent screens and a silver halide radiographic element comprising a support base and front and back silver halide emulsion layers each coated on one surface of said support, wherein said front screen is arranged adjacent to said front silver halide layer and said back screen is arranged adjacent to said back silver halide layer, and wherein

1) said front screen comprises a first radiation emitting phosphor and said front silver halide layer com­prises silver halide grains sensitive to said first radi­ation emitted by said front screen, and

2) said back screen comprises a second radiation emitting phosphor and said back silver halide layer com­prises silver halide grains sensitive to said second ra­diation emitted by said back screen, characterized in that

a) said first radiation emitted by said front screen has a wavelength which differs from said second radiation emitted by said back screen by at least 50 nm,

b) said front silver halide emulsion layer is sub­stantially insensitive to said second radiation emitted by said back screen, and

c) said back silver halide emulsion layer is sub­stantially insensitive to said first radiation emitted by said front screen,

the difference in wavelength region of said first and second radiations and the insensitivity of each silver halide layer to radiation emitted by opposite screen be­ing such to reduce crossover exposure of at least 10 per­cent when compared with a symmetrical combination of a pair of green light emitting fluorescent screens and a double coated green sensitized silver halide emulsion radiographic element.

[0036] According to a preferred embodiment of this inven­tion, in the combination of a pair of front and back ra­diographic fluorescent screens and a double coated silver halide radiographic element, said front screen comprises a non-actinic radiation, preferably green light, emitting phosphor and is arranged adjacent to a front silver halide layer comprising a silver halide emulsion spec­trally sensitized to the radiation emitted by said front screen, and said back screen comprises an actinic radiation, preferably UV light, emitting phosphor and is arranged adjacent to a back silver halide layer compris­ing a silver halide emulsion insensitized to the visually observable regions of the electromagnetic spectrum (that is 410 to 750 nm).

[0037] Preferably, the phosphors used in the front fluores­cent screens applied in the present invention emit radia­tion in the green or red region of the visible spectrum. More preferably, said phosphors emit radiation in the green region of the visible spectrum. Most preferably, said phosphors emit radiation having more than about 80% of its spectral emission above 480 nm and its maximum of emission in the wavelength range of 530-570 nm. Green emitting phosphors which may be used in the front fluo­rescent screens of the present invention include rare earth activated rare earth oxysulfide phosphors of at least one rare earth element selected from yttrium, lan­thanum, gadolinium and lutetium, rare earth activated rare earth oxyhalide phosphors of the same rare earth elements, a phosphor composed of a borate of the above rare earth elements, a phosphor composed of a phosphate of the above rare earth elements and a phosphor composed of tantalate of the above rare earth elements. These rare earth green emitting phosphors have been extensively de­scribed in the patent literature, for example in US Pat­ents 4,225,653, 3,418,246, 3,418,247, 3,725,704, 3,617,743, 3,974,389, 3,591,516, 3,607,770, 3,666,676, 3,795,814, 4,405,691, 4,311,487 and 4,387,141. These rare earth phosphors have a high X-ray stopping power and high efficiency of light emission when excited with X radia­tion and enable radiologists to use substantially lower X radiation dosage levels. Particularly suitable phosphors for use in the front fluorescent screens of the present invention are terbium or terbium-thulium activated rare earth oxysulfide phosphors represented by the general formula (I)
(Ln_1-a-b, Tb_a, Tm_b)2 O₂S       (I)
wherein Ln is at least one rare earth element selected from lanthanum, gadolinium and lutetium, and a and b are numbers such as to meet the conditions 0.0005 ≦ a ≦ 0.09 and 0 ≦ b ≦ 0.01, respectively, and terbium or terbium-­thulium activated rare earth oxysulfide phosphors repre­sented by the general formula (II)
(Y_1-c-a-b, Ln_c, Tb_a, Tm_b)₂O₂S       (II)
wherein Ln is at least one rare earth element selected from lanthanum, gadolinium and lutetium, and a, b and c are numbers such as to meet the conditions 0.0005 ≦ a ≦ 0.09, 0 ≦ b ≦ 0.01 and 0.65 ≦ c ≦ 0.95, respectively.

[0038] Figure 2 shows an emission spectrum of a front fluo­rescent screen comprising a fluorescent layer of (Gd₁₋₀.₀₅, Tb₀.₀₅)₂O₂S phosphor as green emitting phos­phor, expressed as fluorescence (F) versus wavelengths (nm).

[0039] The front silver halide emulsion layer, to be ar­ranged according to this invention adjacent to the front fluorescent screen, comprises silver halide grains which are optically sensitized to the spectral region of the radiation emitted by the screens, preferably to a spec­tral region of an interval comprised within 25 nm from the wavelength of the maximum emission of the screen, more preferably within 15 nm, and most preferably within 10 nm. The silver halide grains of the front silver halide layer have adsorbed on their surface spectral sen­sitizing dyes that exhibit absorption maxima in the re­gions of the visible spectrum where the front fluorescent screen emits. Preferably,spectral sensitizing dyes according to this invention are those which exhibit J aggregates if adsorbed on the surface of the silver halide grains and a sharp absorption band (J-band) with a bathocromic shifting with respect to the absorption maxi­mum of the free dye in aqueous solution. Spectral sensi­tizing dyes producing J aggregates are well known in the art, as illustrated by F. M. Hamer, Cyanine Dyes and Re­lated Compounds, John Wiley and Sons, 1964, Chapter XVII and by T. H. James, The Theory of the Photographic Pro­cess, 4th edition, Macmillan, 1977, Chapter 8.

[0040] In a preferred form, J-band exhibiting dyes are cyanine dyes. Such dyes comprise two basic heterocyclic nuclei joined by a linkage of methine groups. The hetero­cyclic nuclei preferably include fused benzene rings to enhance J aggregation.

[0041] The heterocyclic nuclei are preferably quinolinium, benzoxazolium, benzothiazolium, benzoselenazolium, benz­imidazolium, naphthoxazolium, naphthothiazolium and naph­thoselenazolium quaternary salts.

[0042] J-band type dyes preferably used in the present in­vention have the following general formula (III):

wherein
Z₁ and Z₂ may be the same or different and each rep­resents the elements necessary to complete a cyclic nu­cleus derived from basic heterocyclic nitrogen compounds such as oxazoline, oxazole, benzoxazole, the naphthoxazoles (e.g., naphth{2,1-d}oxazole, naphth{2,3-d}oxazole, and naphth{1,2-d}oxazole), thiazoline, thiazole, benzothiazole, the naphthothiazoles (e.g., naphtho{2,1-d}thiazole), the thiazoloquinolines (e.g., thiazolo{4,5-b}quinoline), selenazoline, selenazole, benzoselenazole, the naphthoselenazoles (e.g., naphtho{1,2-d}selenazole, 3H-indole (e.g., 3,3-dimethyl3H-indole), the benzindoles (e.g., 1,1-dimethylbenzindole), imidazoline, imidazole, benzimidazole, the naphthimidazoles (e.g., naphth{2,3-d}­imidazole), pyridine, and quinoline, which nuclei may be substituetd on the ring by one or more of a wide variety of substituents such as hydroxy, the halogens (e.g., fluoro, bromo, chloro, and iodo), alkyl groups or substi­tuted alkyl groups (e.g., methyl, ethyl, propyl, isoprop­yl, butyl, octyl, dodecyl, 2-hydroxyethyl, 3-sulfopropyl, carboxymethyl, 2-cyanoethyl, and trifluoromethyl), aryl groups or substituted aryl groups (e.g., phenyl, 1-­naphthyl, 2-naphthyl, 4-sulfophenyl, 3-carboxyphenyl, and 4-biphenyl), aralkyl groups (e.g., benzyl and phenethyl), alkoxy groups (e.g., methoxy, ethoxy, and isopropoxy), aryloxy groups (e.g., phenoxy and 1-naphthoxy), alkylthio groups (e.g., ethylthio and methylthio), arylthio groups (e.g., phenylthio, p-tolythio, and 2-naphthylthio), methylenedioxy, cyano, 2-thienyl, styryl, amino or sub­stituted amino groups (e.g., anilino, dimethylanilino, diethylanilino, and morpholino), acyl groups (e.g., acet­yl and benzoyl), and sulfo groups,

[0043] R₁ and R₂ can be the same or different and represent alkyl groups, aryl groups, alkenyl groups, or aralkyl groups, with or without substituents, (e.g., carboxy­methyl, 2-hydroxyethyl, 3-sulfopropyl, 3-sulfobutyl, 4-­sulfobutyl, 2-methoxyethyl, 2-sulfatoethyl, 3-thiosul­fatoethyl, 2-phosphonoethyl, chlorophenyl, and bromophen­yl), R₃ represents a hydrogen atom,
R₄ and R₅ can be the same or different and represent a hydrogen atom or a lower alkyl group of from 1 to 4 carbon atoms,
p and q are 0 or 1, except that both p and q prefer­ably are not 1,
m is 0 or 1 except that when m is 1 both p and q are 0 and at least one of Z₁ and Z₂ represents imidazoline, oxazoline, thiazoline, or selenazoline,
A is an anionic group,
B is a cationic group, and
k and 1 may be 0 or 1, depending on whether ionic substituents are present. Variants are, of course, possi­ble in which R₁ and R₃, R₂ and R₅, or R₁ and R₂ together represent the atoms necessary to complete an alkylene bridge.

[0044] In the most preferred form of this invention, where­in the phosphors of the front fluorescent screen are rare earth phosphors emitting in the green region of the visi­ble spectrum, said optical sensitizing dyes adsorbed on said silver halide grains of the front silver halide lay­er are represented by the following general formula (IV):

wherein
R₁₀ represents a hydrogen atom or a lower alkyl group of from 1 to 4 carbon atoms (e.g. methyl, and eth­yl),
R₆, R₇, R₈ and R₉ each represents a hydrogen atom, a halogen atom (e.g. chloro, bromo, iodo, and fluoro), a hydroxy group, an alkoxy group (e.g. methoxy and ethoxy), an amino group (e.g. amino, methylamino, and dimethyl­amino), an acylamino group (e.g. acetamido and propion­amido), an acyloxy group (e.g. acetoxy group), an alkoxy­carbonyl group (e.g. methoxycarbonyl, ethoxycarbonyl, and butoxycarbonyl), an alkyl group (e.g. methyl, ethyl, and isopropyl), an alkoxycarbonylamino group (e.g. ethoxy­carbonylamino) or an aryl group (e.g. phenyl and tolyl), or, together, R₆ and R₇ and, respectively, R₈ and R₉ can be the atoms necessary to complete a benzene ring (so that the heterocyclic nucleus results to be, for example, an α-naphthoxazole nucleus, a β-naphthoxazole or a β,β′-­naphthoxazole),
R₁₁ and R₁₂ each represents an alkyl group (e.g. methyl, propyl, and butyl), a hydroxyalkyl group (e.g. 2-­hydroxyethyl, 3-hydroxypropyl, and 4-hydroxybutyl), an acetoxyalkyl group (e.g. 2-acetoxyethyl and 4-acetoxybut­yl), an alkoxyalkyl group (e.g. 2-methoxyethyl and 3-­methoxypropyl), a carboxyl group containing alkyl group (e.g. carboxymethyl, 2-carboxyethyl, 4-carboxybutyl, and 2-(2-carboxyethoxy)-ethyl), a sulfo group containing alk­yl group (e.g. 2-sulfoethyl, 3-sulfopropyl, 4- sulfobut­yl, 2-hydroxy3- sulfopropyl, 2-(3-sulfopropoxy)-propyl, p-sulfobenzyl, and p-sulfophenethyl), a benzyl group, a phenetyl group, a vinylmethyl group, and the like,
X⁻ represents an acid anion (e.g. a chloride, bro­mide, iodide, thiocyanate, methylsulfate, ethylsulfate, perchlorate, and p-toluensulfonate ion), and
n represents 1 or 2.

[0045] The alkyl groups included in said substituents R₆, R₇, R₈, R₉, R₁₀, and R₁₁ and, more particularly, the alk­yl portions of said alkoxy, alkoxycarbonyl, alkoxycarbon­ylamino, hydroxyalkyl, acetoxyalkyl groups and of the alkyl groups associated with a carboxy or sulfo group each preferably contain from 1 to 12, more preferably from 1 to 4 carbon atoms, the total number of carbon at­oms included in said groups preferably being no more than 20.

[0046] The aryl groups included in said substituents R₆, R₇, R₈ and R₉ each preferably contain from 6 to 18, more preferably from 6 to 10 carbon atoms, the total number of carbon atoms included in said groups arriving up to 20 carbon atoms.

[0047] The following are specific examples of J-band sensi­tizing dyes belonging to those represented by the general formula (IV) above:

[0048] Figure 3 shows the sensitivity spectrum of a front silver halide layer comprising silver bromoiodide grains comprising 2.3 mole percent iodide and having adsorbed on their surface the optical sensitizing dye A above, ex­pressed as sensitivity (S) versus wavelengths (nm).

[0049] Preferably, the phosphors used in the back fluores­cent screens applied in the present invention emit radia­tion in the ultraviolet region of the electromagnetic spectrum. More preferably, said phosphors emit radiation having more than about 80% of their spectral emission below 410 nm and their maximum of emission in the wavelength range of 300-360 nm. Ultraviolet emitting phosphors which may be used in the back fluorescent screens of the present invention include ultraviolet emitting phosphors known in the art such as lead or lanthanum activated barium sulfate phosphors, barium fluorohalide phosphors, lead activated barium silicate phosphors, gadolinium activated yttrium oxide phosphors, barium fluoride phosphors, alkali metal activated rare earth niobate or tantalate phosphors etc. Ultraviolet emitting phosphors are described for example in BE 703,998 and 757,815, in EP 202,875 and by Buchanan et al., J. Applied Physics, vol. 9, 4342-4347, 1968,and by Clapp and Ginther, J. of the Optical Soc. of America, vol. 37, 355-362, 1947. Particularly suitable ultraviolet emitting phosphors for use in the back fluorescent screens of the present invention are those represented by the general formula (V)
(Y_1-2/3x-1/3y, Sr_x, Li_y) TaO₄
wherein x and y are numbers such as to meet the condi­tions 10⁻⁵ ≦ x ≦ 1 and 10⁻⁴ ≦ y ≦ 0.1as described in EP 202,875.

[0050] Figure 4 shows an emission spectrum of a back fluo­rescent screen comprising a fluorescent layer of (Y, Sr, Li)TaO₄ phosphor as ultraviolet emitting phosphor, ex­pressed as fluorescence (F) versus wavelengths (nm).

[0051] The back silver halide emulsion layer, arranged ac­cording to this invention adjacent to the back actinic light emitting phosphor screen, comprises silver halide grains which are not optically sensitized but possess the inherent spectral sensitivity of the known types of photosensitive silver halides. Said inherent spectral sensitivity of the conventional silver halide emulsions used in photographic films as known ranges in the ultraviolet and blue region of the electromagnetic spectrum.

[0052] Figure 5 shows the sensitivity spectrum of a back silver halide emulsion layer comprising silver bromo­iodide grains comprising 2.3 percent mole iodide and hav­ing no optical sensitizing dye adsorbed on their surface, expressed as sensitivity (S) versus wavelenghts (nm).

[0053] According to the present invention, the non-actinic radiation (preferably green light) emitted by the front screen imagewise exposes the adjacent front silver halide layer comprising silver halide grains optically sensi­tized to the radiation emitted by said screens. Part of said non-actinic radiation reaches the opposite back sil­ver halide layer but does not crossover expose the silver halide grains of the back silver halide layer as those grains are not optically sensitized to the radiation emitted by said front screen. The ultraviolet or blue emission of the back fluorescent screen undergoes absorp­tion by the adjacent back silver halide layer and imagewise exposes the silver halide grains which are not optically sensitized, rather than crossover passing to the opposite front silver halide layer. This is due to the fact that silver halide grains possess a good inher­ent absorption of light with a wavelength below 500 nm and a strong light scattering of ultraviolet and blue light through the dispersed silver halide particles of the emulsion layer. The above implies not having a large amount of ultraviolet or blue light of the back fluores­cent screen to expose the opposite front silver halide layer. The crossover exposure reduction attained with the screen pair and double silver halide element combination of this invention is preferably at least 10 percent, more preferably at least 20 percent in comparison with a con­ventional combination of green emitting fluorescent screens and double coated green sensitized silver halide radiographic element. Accordingly, the image sharpness is improved by reducing crossover exposure using a unique combination of conventional silver halide emulsion layers and fluorescent screens.

[0054] The light-sensitive double-side coated silver halide radiographic element comprises a transparent polymeric base of the type commonly used in radiography, for in­stance a polyester base, and in particular a polyethylene terephthalate base.

[0055] In the silver halide photographic elements of this invention, the silver halide emulsions coated on the two surfaces of the support, the front optically sensitized silver halide emulsion and the back optically unsensi­tized silver halide emulsion, may be similar or different and comprise emulsions commonly used in photographic ele­ments, such as silver chloride, silver iodide, silver chloro-bromide, silver chloro-bromo-iodide, silver bro­mide and silver bromo-iodide, the silver bromoiodide be­ing particularly useful for radiographic elements. The silver halide grains may have different shapes, for in­stance cubic, octahedrical, tabular shapes, and may have epitaxial growths; they generally have mean sizes ranging from 0.1 to 3 µm, more preferably from 0.4 to 1.5 µm. The emulsion are coated on the support at a total silver cov­erage comprised in the range from about 3 to 6 grams per square meter. The silver halide binding material used is a water-permeable hydrophilic colloid, which preferably is gelatin, but other hydrophilic colloids, such as gela­tin derivatives, albumin, polyvinyl alcohols, alginates, hydrolized cellulose esters, hydrophilic polyvinyl poly­mers, dextrans, polyacrylamides, hydrophilic acrylamide copolymers and alkylacrylates can also be used alone or in combination with gelatin.

[0056] As regards the processes for silver halide emulsion preparation and use of particular ingredients in the emulsion and in the light-sensitive element, reference is made to Research Disclosure 18,431 published in August 1979, wherein the following chapters are dealt with in deeper details:

IA. Preparation, purification and concentration methods for silver halide emulsions.

IB. Emulsion types.

IC. Crystal chemical sensitization and doping.

II. Stabilizers, antifogging and antifolding agents.

IIA. Stabilizers and/or antifogging.

IIB. Stabilization of emulsions chemically sensitized with gold compounds.

IIC. Stabilization of emulsions containing polyalkylene oxides or plasticizers.

IID. Fog caused by metal contaminants.

IIE. Stabilization of materials comprising agents to in­crease the covering power.

IIF. Antifoggants for dichroic fog.

IIG. Antifoggants for hardeners and developers comprising hardeners.

IIH. Additions to minimize desensitization due to fold­ing. III. Antifoggants for emulsions coated on polyester bas­es.

IIJ. Methods to stabilize emulsions at safety lights.

IIK. Methods to stabilize X-ray materials used for high temperature, Rapid Access, roller processor trans­port processing.

III. Compounds and antistatic layers.

IV. Protective layers.

V. Direct positive materials.

VI. Materials for processing at room light.

IX. Spectral sensitization.

X. UV sensitive materials.

XII. Bases.

[0057] The silver halide photothermographic elements of this invention basically comprise a light insensitive, reducible silver source, a light sensitive material which generates silver when irradiated, and a reducing agent for the silver source. The light sensitive material is generally photographic silver halide which must be in catalytic proxymity to the light insensitive silver source. Catalytic proximity is an intimate physical asso­ciation of these two materials so that when silver specks or nuclei are generated by the irradiation or light expo­sure of the photographic silver halide, those nuclei are able to catalyze the reduction of the silver source by the reducing agent. It has been long understood that sil­ver is a catalyst for the reduction of silver ions and the silver-generating light sensitive silver halide cata­lyst progenitor may be placed into catalytic proximity with the silver source in a number of different fashions, such as partial metathesis of the silver source with a halogen-containing source (e.g. US Pat. No. 3,457,075), coprecipitation of the silver halide and silver source material (e.g. US Pat. No. 3,839,049), and any other method which intimately associates the silver halide and the silver source.

[0058] The silver source used in this area of technology is a material which contains a reducible source of silver ions. The earliest and still preferred source comprises silver salts of long chain fatty carboxylic acids, usual­ly of from 10 to 30 carbon atoms. The silver salt of be­henic acid or mixtures of acids of like molecular weight have been primarily used. Salts of other organic acids or other organic materials such as silver imidazolates have been proposed, and British Pat. No. 1,110,046 discloses the use of complexes of inorganic or organic silver salts as image source materials. Silver salts of long chain (10 to 30, preferably 15 to 28 carbon atoms) fatty carboxylic acids are preferred in the practice of the present inven­tion.

[0059] Photothermographic emulsions are usually constructed as one or two layers per side of the support. Single lay­er construction must contain the silver source material, the silver halide, the developer and binder as well as optional additional materials such as toners, coating aids and other adjuvants. Two-layer constructions must contain the silver source and the silver halide in an emulsion layer (usually the layer adjacent the support) and the other ingredients in the second layer or both layers. The silver source material should constitute from about 20 to 70 percent by weight of the imaging layer. Preferably it is present as 30 to 55 percent by weight. The second layer in a two-layer construction would not affect the percentage of the silver source material de­sired in the single imaging layer.

[0060] The silver halide may be any photosensitive silver halide as silver bromide, silver iodide, silver chloride, silver bromoiodide, silver chlorobromoiodide, silver chlorobromide, etc., and may be added to the emulsion layer in any fashion which places it in catalytic proxim­ity to the silver source. The silver halide is generally present as 0.75 to 15 percent by weight of the imaging layer, although larger amounts are useful. It is pre­ferred to use from 1 to 10 percent by weight silver halide in the imaging layer and most preferred to use from 1.5 to 7.0 percent. The vast list of photographic adjuvants and processing aids may be used in silver halide emulsion preparation. These materials include chemical sensitizers (including sulfur and gold com­pounds), development accelerators (e.g. onium and poly­onium compounds), alkylene oxide polymer accelerators, antifoggant compounds, stabilizers (e.g. azaindenes, es­pecially the tetra- and pentaazaindenes), surface active agents (particularly fluorinated surfactants), antistatic agents (particularly fluorinated compounds), plasticiz­ers, matting agents, and the like.

[0061] The reducing agent for the silver ion may be any materi­al, preferably organic material, which will reduce silver ion to metallic silver. Conventional photographic devel­opers such as phenidone, hydroquinones, and cathecol are useful, but hindered phenol reducing agents are pre­ferred. The reducing agents should be present as 1 to 20 percent by weight of the imaging layer. In a two-layer construction, if the reducing agent is in the second lay­er, slighty higher proportions, of from about 2 to 20 percent tend to be more desirable.

[0062] Toners such as phthalazinone, phthalazine and phthalic acid are not essential to the construction, but highly desirable. These materials may be present, for example, in amounts of from 0.2 to 5 percent by weight.

[0063] The binder may be selected from any of the well known natural and synthetic resins such as gelatin, poly­vinyl acetals, polyvinyl chloride, polyvinyl acetate, cellulose acetate, polyolefins, polyesters, polystyrene, polyacrylonitrile, polycarbonates, and the like. Copoly­mers and terpolymers are, of course, included in these definitions. The polyvinyl acetals, such as polyvinyl butyral and polyvinyl formal, and vinyl copolymers, such as polyvinyl acetate/chloride are particularly desirable. The binders are generally used in a range of 20 to 75 percent by weight of each layer, and preferably about 30 to 55 percent by weight.

[0064] As previously noted, various other adjuvants may be added to the photothermographic emulsions of the present invention. For example, toners, accelerators, acutance dyes, sensitizers, stabilizers, surfactants, lubricants, coating aids, antifoggants, leuco dyes, chelating agents, and various other well known additives may be usefully incorporated. The use of acutance dyes matched to the spectral emission of the intensifying screen is particu­larly desirable.

[0065] The balance in properties of the photothermographic emulsion must be precisely restricted by the proportions of materials in the emulsion. The proportions of the sil­ver salt and organic acid are particularly critical in obtaining necessary sensitometric properties in the pho­tothermographic element for radiographic use. In conven­tional photothermographic emulsions, it is common to use approximately pure salts of organic acids (e.g., behenic acid, stearic acid and mixtures of long chain acids) as the substantive component of the emulsion. Sometimes mi­nor amounts or larger amounts of the acid component are included in the emulsion. In the practice of the present invention the molar ratio of organic silver salt to or­ganic acid must be in the range of 1.5/1 to 6.2/1 (salt/acid). Below that range, the contrast has been found to be too low, and above that range the speed and background stability of the emulsion drop off unaccept­ably. It is preferred that the ratio be in the range of 2.0/1 to 3.50/1.

[0066] The silver halide may be provided by in situ halidi­zation or by use of pre-formed silver halide.

[0067] The process of industrial radiography would be per­formed by using a conventional X-ray projection source or other high energy particle radiation sources including gamma and neutron sources. As well known in the art, the particular phosphors used have a high absorption coeffi­cient for the radiation emitted from the source. Usually this radiation is high energy particle radiation which is defined as any of X-rays, neutrons and gamma radiation. The industrial material would be placed between the con­trollable source of X-rays and the industrial radiograph­ic system of the present invention. A controlled exposure of X-rays would be directed from the source and through the industrial material so as to enter and impact the radiographic system at an angle approximately perpendicu­lar to the plane or surface of the intensifying screens and the photothermographic film contiguous to the inside surface of the screens. The radiation absorbed by the phosphors of the screens would cause light to be emitted by the screens which in turn would generate a latent im­age in the silver halide grains of the two emulsion lay­ers. Conventional thermal development would then be used on the exposed film.

[0068] The X radiation image converting screens of this invention have a fluorescent layer comprising a binder and a phosphor dispersed therein. The fluorescent layer is formed by dispersing the phosphor in the binder to prepare a coating dispersion, and then applying the coat­ing dispersion by a conventional coating method to form a uniform layer. Although the fluorescent layer itself can be a radiation image converting screen when the fluores­cent layer is self-supporting, the fluorescent layer is generally provided on a substrate to form a radiation image converting screen. Further, a protective layer for physically and chemically protecting the fluorescent lay­er is usually provided on the surface of the fluorescent layer. Furthermore, a primer layer is sometimes provided between the fluorescent layer and the substrate to close­ly bond the fluorescent layer to the substrate, and a reflective layer is sometimes provided between the sub­strate (or the primer) and the fluorescent layer.

[0069] The binder employed in the fluorescent layer of the X radiation image converting screens of the present in­vention, can be, for example, one of the binders commonly used in forming layers: gum arabic, protein such as gela­tin, polysaccharides such as dextran, organic polymer binders such as polyvinylbutyral, polyvinylacetate, nitrocellulose, ethylcellulose, vinylidene-chloride-vin­ylchloride copolymer, polymethylmethacrylate, polybutyl­methacrylate, vinylchloride-vinylacetate copolymer, poly­urethane, cellulose acetate butyrate, polyvinyl alcohol, and the like.

[0070] Generally, the binder is used in an amount of 0.01 to 1 part by weight per one part by weight of the phos­phor. However, from the viewpoint of the sensitivity and the sharpness of the screen obtained, the amount of the binder should preferably be small. Accordingly, in con­sideration of both the sensitivity and the sharpness of the screen and the easiness of application of the coating dispersion, the binder is preferably used in an amount of 0.03 to 0.2 parts by weight per one part by weight or the phosphor. The thickness of the fluorescent layer is gen­erally within the range of 10 µm to 1 mm.

[0071] In the radiation image converting screens of the present invention, the fluorescent layer is generally coated on a substrate. As the substrate, various materi­als such as polymer material, glass, wool, cotton, paper, metal, or the like can be used. From the viewpoint of handling the screen, the substrate should preferably be processed into a sheet or a roll having flexibility. In this connection, as the substrate is preferably either a plastic film (such as a cellulose triacetate film, poly­ester film, polyethylene terephthalate film, polyamide film, polycarbonate film, or the like), or ordinary paper or processed paper (such as a photographic paper, baryta paper, resin-coated paper, pigment-containing paper which contains a pigment such as titanium dioxide, or the like). The substrate may have a primer layer on one sur­face thereof (the surface on which the fluorescent layer is provided) for the purpose of holding the fluorescent layer tightly. As the material of the primer layer, an ordinary adhesive can be used. In providing a fluorescent layer on the substrate (or on the primer layer or on the reflective layer), a coating dispersion comprising the phosphor dispersed in a binder may be directly applied to the substrate (or to the primer layer or to the reflec­tive layer).

[0072] Further, in the X radiation image converting screens of the present invention, a protective layer for physi­cally and chemically protecting the fluorescent layer is generally provided on the surface of the fluorescent lay­er intended for exposure (on the side opposite the sub­strate). When, as mentioned above, the fluorescent layer is self-supporting, the protective layer may be provided on both surfaces of the fluorescent layer. The protective layer may be provided on the fluorescent layer by direct­ly applying thereto a coating dispersion to form the pro­tective layer thereon, or may be provided thereon by bonding thereto the protective layer formed beforehand. As the material of the protective layer, a conventional material for a protective layer such a nitrocellulose, ethylcellulose, cellulose acetate, polyester, polyethyl­ene terephthalate, and the like can be used.

[0073] The X radiation image converting screens of the present invention may be colored with a colorant. Fur­ther, the fluorescent layer of the radiation image con­verting screen of the present invention may contain a white powder dispersed therein. By using a colorant or a white powder, a radiation image converting screen which provides an image of high sharpness can be obtained.

EXAMPLES

[0074] The invention can be better illustrated by reference to the following specific examples and comparative inves­tigations.

Green Emitting Phosphor Screen GRS₁

[0075] A high resolution green emitting phosphor screen, screen GRS₁, was prepared consisting of a (Gd₁₋₀.₀₅, Tb₀.₀₅)₂O₂S phosphor with average particle grain size of 3 µm coated in a hydrophobic polymer binder at a phosphor coverage of 270 g/m² and a thickness of 70 µm on a poly­ester support. Between the phosphor layer and the support a reflective layer of TiO₂ particles in a poly(urethane) binder was coated. The screen was overcoated with a cel­lulose triacetate layer.

Green Emitting Phosphor Screen GRS₂

[0076] A medium resolution green emitting phosphor screen, screen GRS₂, was prepared consisting of a (Gd₁₋₀.₀₅, Tb₀.₀₅)₂O₂S phosphor with average particle grain size of 4 µm coated in a hydrophobic polymer binder at a phosphor coverage of 480 g/m² and a thickness of 120 µm on a poly­ester support. Between the phosphor layer and the support a reflective layer of TiO₂ particles in a poly(urethane) binder was coated. The screen was overcoated with a cel­lulose triacetate layer.

UV Emitting Phosphor Screen UVS₃

[0077] An UV emitting phosphor screen, screen UVS₃, was prepared consisting of the type NP-3040 (Y, Sr, Li)TaO₄ phosphor of Nichia Kagaku Kogyo K.K. with average parti­cle grain size of 5.1 µm coated in a hydrophobic polymer binder at a phosphor coverage of 450 g/m² and a thickness of 110 µm on a polyester support. Between the phosphor layer and the support a reflective layer of TiO₂ parti­cles in a poly(urethane) binder was coated. The screen was overcoated with a cellulose triacetate layer.

Light-sensitive Photographic Film GRUVF₁

[0078] A light-sensitive film having a green sensitized silver halide emulsion layer (hereinafter designated front layer) coated on one side of the support and a spectrally unsensitized silver halide emulsion layer (hereinafter designated back layer) coated on the other side of the support, film GRUVF₁, was prepared in the following manner. On one side of a polyester support was coated a green sensitized silver halide gelatin emulsion layer containing cubic silver bromoiodide grains (having 2.3 mole percent iodide and an average grain size of 0.65 µm) at 2.57 g/m² Ag and 1.9 g/m² gelatin. The emul­sion was sulfur and gold chemically sensitized and spec­trally sensitized with 1,070 mg/ mole Ag of the green sensitizing Dye A, anhydro-5,5′-dichloro-9-ethyl-­3,3′-bis(3-sulfopropyl)-oxacarbocyanine hydroxyde tri­ethylamine salt. A protective overcoat containing 0.9 g/m² gelatin was applied to said silver bromoiodide front layer. On the other side of the polyester support was coated a spectrally unsensitized silver halide silver halide gelatin emulsion layer containing cubic silver bromoiodide grains (comprising a 1:1 by weight blend of silver bromoiodide grains having 2 mole percent iodide and an average grain size of 1.3 µm and silver bromo­iodide grains having 2.3 mole percent iodide and an av­erage grain size of 0.65 µm) at 2.51 g/m² Ag and 1.8 g/m² gelatin. The emulsion was sulfur and gold chemically sen­sitized. A protective overcoat containing 0.9 g/m² gela­tin was applied to said silver bromoiodide back layer.

Light-sensitive Photographic Film GRUVF₂

[0079] A light-sensitive film having a green sensitized silver halide emulsion layer (hereinafter designated front layer) coated on one side of the support and a spectrally unsensitized silver halide emulsion layer (hereinafter designated back layer) coated on the other side of the support, film GRUVF₂, was prepared in the following manner. On one side of a polyester support was coated the green sensitized silver halide gelatin emul­sion layer containing cubic silver bromoiodide grains of the front layer of film GRUVF₁ (having 2.3 mole percent iodide and an average grain size of 0.65 µm) at 2.60 g/m² Ag and 1.9 g/m² gelatin. The emulsion was sulfur and gold chemically sensitized and spectrally sensitized with 1,070 mg/Ag mole of the green sensitizing Dye A, an­hydro-5,5′-dichloro-9-ethyl-3,3′-bis(3-sulfopropyl)- oxa­carbocyanine hydroxyde triethylamine salt. A protective overcoat containing 0.9 g/m² gelatin was applied to said silver bromoiodide front layer. On the other side of the polyester support was coated a spectrally unsensitized silver halide silver halide gelatin emulsion layer con­taining cubic silver bromoiodide grains of the front lay­er of film GRUVF₁ (having 2.3 mole percent iodide and an average grain size of 0.65 µm) at 2.49 g/m² Ag and 1.9 g/m² gelatin. The emulsion was sulfur and gold chemically sensitized. A protective overcoat containing 0.9 g/m² gelatin was applied to said silver bromoiodide back lay­er.

Light-sensitive Photographic Film UVUVF₃

[0080] A light-sensitive film having a spectrally unsensi­tized silver halide emulsion layer coated on each side of a support, film UVUVF₃, was prepared in the following manner. On each side of a polyester support was coated a spectrally unsensitized silver halide silver halide gela­tin emulsion layer containing cubic silver bromoiodide grains of the front layer of film GRUVF₁ (having 2.3 mole percent iodide and an average grain size of 0.65 µm) at 2.60 and 2.49 g/m² Ag, respectively, and 1.9 g/m² gela­tin. The emulsion was sulfur and gold chemically sensi­tized. A protective overcoat containing 0.9 g/m² gelatin was applied to each silver bromoiodide layer.

Light-sensitive Photographic Film GRGRF₄

[0081] A light-sensitive film having a green sensitized silver halide emulsion layer coated on each side of a support, film GRGRF₄, was prepared in the following man­ner. On each side of a polyester support was coated the green sensitized silver halide gelatin emulsion layer containing cubic silver bromoiodide grains of the front layer of film GRUVF₁ (having 2.3 mole percent iodide and an average grain size of 0.65 µm) at 2.18 g/m² Ag and 1.9 g/m² gelatin. The emulsion was sulfur and gold chemi­cally sensitized and spectrally sensitized with 1,070 mg/­mole Ag of the green sensitizing Dye A, anhydro-5,5′-di­chloro-9-ethyl-3,3′-bis(3-sulfopropyl)- oxacarbocyanine hydroxyde triethylamine salt. A protective overcoat con­taining 0.9 g/m² gelatin was applied to each silver bromoiodide layer.

Comparison of Screen Pairs and Light-sensitive Photo­graphic Films

[0082] Pairs of screens in combination with double coated light-sensitive photographic films described above were exposed as follows. Referring to Figure 1, film-screens combinations were made in which the front screen was in contact with the front emulsion layer and the back screen was in contact with the back emulsion layer. Each screen pair-film combination was exposed to X-rays from a tung­sten target tube operated at 80 kVp and 25 mA from a distance of 120 cm. The X-rays passed through an aluminium step wedge before reaching the screen-film com­bination. Following exposure the films were processed in a 3M Trimatic^TM XP507 processor using 3M XAD/2 developer replenisher and 3M XAF/2 fixer replenisher.

[0083] The speed and the image quality are reported in the following table. Percent crossover was calculated by us­ing the following equation:

wherein δ logE is the difference in speed between the two emulsion layers of the same film when exposed with a single screen (the lower the percent crossover, the bet­ter the image quality).

TABLE

Comb.	Screen Pair Front/Back	Film	Rel. Speed log E	% Crossover
1	GRS₁/GRS₁	GRGRF₄	0.00	37
2	UVS₃/UVS₃	UVUVF₃	-0.39	9
3	GRS₁/UVS₃	GRUVF₂	-0.22	4*	9**
4	GRS₁/UVS₃	GRUVF₁	0.00	9*	5**
5	GRS₂/UVS₃	GRUVF₁	+0.18	4*	5**

* crossover measured in the front emulsion layer

** crossover measured in the back emulsion layer

[0084] Sharpness and granularity of the screen pair-film combinations were determined as follows. Each screen pair-film combination was exposed to X-rays from a tung­sten tube operated at 80 kVp and 25 mA from a distance of 150 cm. The X-rays passed through a 100 µ thick lead Funk target sold by Huttner Company before reaching the screen-film combination. Following exposure the films were processed in the 3M Trimatic^TM XP507 processor using 3M XAD/2 developer replenisher and 3M XAF/2 fixer reple­nisher. Sharpness and granularity of the processed films were determined by visual examination of ten observers skilled in making image comparisons. Figures 6 and 7 are graphs illustrating the sharpness (SH) and granularity (GR) versus the difference of sensitivity δS of the dou­ble coated silver halide element and fluorescent screen pair combinations and that of green sensitive double coated element combined with green emitting fluorescent screen pair taken as reference. In the graphs, the higher the numbers of sharpness and granularity, the better is the sharpness and granularity. Sharpness and granularity of the UV and blue light sensitive double coated silver halide element combined with UV emitting fluorescent screen pair are the best but at the lower level of sensi­tivity, while sharpness and granularity of the double coated element and screen pair combinations of this in­vention are better or comparable to that of green sensi­tive double coated element combined with green emitting fluorescent screen pair at comparable or higher level of sensitivity.

Light-sensitive Photothermographic Film GRBLF₅

a) Preparation of the silver soap.

[0085] To 20 l of water at 80°C were added 634.5 g of Humbo acid 9022 (a long chain fatty carboxylic acid comprising 90% C₂₀ + C₂₂, 5% C₁₈ and 5% other acid), 131 g Humbo acid 9718 (a long chain fatty carboxylic acid comprising 95% C₁₈ and 5% C₁₆) and 0.44 moles of a 0.08 µm cubic silver bromoiodide (6% mole iodide) emulsion. While stirring, were added 89.18 g NaOH dissolved in 1.25 l water, then 19 ml of conc. HNO₃ diluted with 50 ml water. At 55°C were added 364.8 g AgNO₃ dissolved in 2.5 l water at 55°C. The mixture was heated at 55°C for one hour while stirring slowly, centrifugated while spray washing until 20,000 ohms resistance of water was obtained and dried.

b) Preparation of the silver salt homogenate.

[0086] Silver soap powder above (12% by weight), toluene (20% by weight) and methylethyl ketone (68% by weight) were mixed, soaked over-night, added with 12 g polyvinylbutyral (Butwar^TM B-76) and homogenized at 4,000, then 8,000 PSI.

c) Preparation of the first trip.

[0087] 200 g of the silver soap homogenate above were added with 40 g methylethyl ketone and 30 g polyvinylbutyral (Butwar^TM B-76) and mixed for one-half hour. The mixture was added with 2.2 ml of a 10% HgBr₂ in methanol, stirred for 5 minutes, then added with 4 g of Nonox^TM W₅₀ Devel­oper of formula

[0088] One 50 g part of the dispersion above was added with 0.6 ml of a solution of 0.04 g per 10 ml of the following blue sensitizer

[0089] A second 50 g part of the dispersion above was added with 0.6 ml of a solution of 0.05 g per 10 ml of the fol­lowing green sensitizer

d) Coating of the first trip.

[0090] The blue sensitized dispersion above was coated on a clear 4 mil (2 x 10⁻⁴ m) polyethyleneterephthalate sup­port at 5 mils over the support and dried for 3 minutes at 87°C. On the opposite side of the support the green sensitized dispersion above was coated at 5 mils over the support and dried for 3 minutes at 87°C.

e) Preparation of the second trip.

[0091] 

	Component	Parts by Weight
A.	Methylethyl ketone	78.58
B.	Acetone	12.02
C.	Methanol	4.91
D.	FC-431 (3M Fluorocarbon)	0.04
E.	Phthalazine	0.59
F.	4-Methyl-phthalic acid	0.41
G.	Tetrachlorophthalic anhydride	0.27
H.	Tetrachlorophthalic acid	0.12
I.	Cellulose acetate ester	3.06

A through H were added to a container and mixed until solids were dissolved. I was then added and mixed for one hour until was dissolved.

f) Coating of the second trip.

[0092] On the blue sensitizing coating previously applied, the second trip was coated over the first at 2.25 mils and dried for 3 minutes at 87°C. The film was turned over and, on the green sensitized coating previously applied, the second trip was coated at 2.25 mils and dried for 3 minutes at 87°C.

g) Evaluation of the film.

[0093] A sample of the finished double-side coated photo­thermographic film was exposed with a xenon flash sensi­tometer through a 460 nanometer narrow band filter at a setting of 10⁻³ seconds through a 0-4 continous density wedge. The exposed sample was processed for four seconds at 131°C in a roller driven thermal processor. The sensitometry was recorded as D_min=0.21 and D_max=4.22. Another sample was exposed and processed as above but using a 560 nanometer narrow band filter. The sensitometry was recorded as D_min=0.21 and D_max=2.19. Clearly there is no cross-over from the green sensitized layer to the blue sensitizing layer. The blue sensitized layer when coated singly on one side of a polyester sub­strate recorded an image as follows : D_min=0.13 and D_max=2.56.

Claims

1. A combination of photosensitive elements for use in radiography comprising two separate front and back X-ray fluorescent screens and a silver halide radiograph­ic element comprising a support base and front and back silver halide emulsion layers each coated on one surface of said support, wherein said front screen is arranged adjacent to said front silver halide layer and said back screen is arranged adjacent to said back silver halide layer, and wherein
1) said front screen comprises a first radiation emit­ting phosphor and said front silver halide layer comprises silver halide grains sensitive to said first radiation emitted by said front screen, and
2) said back screen comprises a second radiation emit­ting phosphor and said back silver halide layer com­prises silver halide grains sensitive to said second radiation emitted by said back screen,
characterized in that
a) said first radiation emitted by said front screen is in a wavelength region of non-actinic radiation and said second radiation emitted by said back screen is in a wavelength region of actinic radiation,
b) said first radiation emitted by said front screen has a wavelength which differs from said second radiation emitted by said back screen by at least 50 nm,
c) said front silver halide emulsion layer is substan­tially insensitive to said second radiation emitted by said back screen, and
d) said back silver halide emulsion layer is sub­ stantially insensitive to said first radiation emit­ted by said front screen,
the difference in wavelength region of said first and second radiations and the insensitivity of each silver halide layer to radiation emitted by opposite screen be­ing such to reduce crossover exposure of at least 10 per­cent when compared with a symmetrical combination of a pair of green light emitting fluorescent screens and a double coated green sensitized silver halide radiograph­ic element.

2. The combination of claim 1, wherein

a) said front screen comprises a non-actinic light emitting phosphor and said front silver halide layer comprises silver halide grains spectrally sensitized to the radiation emitted by said front screen, and

b) said back screen comprises a UV emitting phosphor and said back silver halide layer comprises spec­trally insensitized silver halide grains.

3. The combination of claim 1, wherein said front screen comprises a substantially green emitting phosphor.

4. The combination of claim 1, wherein said front screen comprises a green emitting phosphor having more than 80% of its spectral emission above 480 nm and its maximum of emission in the wavelength range of 530 - 570 nm.

5. The combination of claim 1, wherein said front screen comprises a green emitting phosphor represented by the general formula
(Ln_1-a-b, Tb_a, Tm_b)₂O₂S
wherein Ln is at least one rare earth selected from lanthanium, gadolinium and lutetium, and a and b are num­bers such as to meet the conditions of 0.0005 ≦ a ≦ 0.09 and 0 ≦ b ≦ 0.01, respectively, or the general formula
(Y_1-c-a-b,Ln_c,Tb_a,Tm_b)₂O₂S
wherein Ln is at least one rare earth selected from lan­thanium, gadolinium and lutetium, and a, b and c are num­bers such as to meet the conditions of 0.0005 ≦ a ≦ 0.09, 0 ≦ b ≦ 0.01 and 0.65 ≦ c ≦ 0.95, respectively.

6. The combination of claim 1, wherein said front screen comprises a terbium-activated gadolinium or lan­thanium oxysulphide phosphor having substantially emis­sion peaks at 487 and 545 nm.

7. The combination of claim 1, wherein said front silver halide layer comprises silver halide grains spec­trally sensitized with spectral sensitizing dyes of the cyanine or merocyanine dyes.

8. The combination of claim 4, wherein said front silver halide layer comprises silver halide grains spec­trally sensitized with sensitizing dyes in such a way that it is sensitive for light in wavelength range of 530 - 570 nm.

9. The combination of claim 4, wherein said front silver halide emulsion layer comprises silver halide grains spectrally sensitized with sensitizing dyes repre­sented by the general formula

wherein R₁₀ represents a hydrogen atom or an alkyl group, R₆, R₇, R₈ and R₉ each represent a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group, an amino group, an acylamino group, an acyloxy group, an alkoxycarbonyl group, an alkyl group, an alkoxycarbonyl­amino group or an aryl group, or, together, R₆ and R₇, and respectively R₈ and R₉ can be the atoms necessary to complete a benzene ring, R₁₁ and R₁₂ each represent an alkyl group, a hydroxyalkyl group, an acetoxyalkyl group, an alkoxyalkyl group, a carboxyl group containing alkyl group, a sulfo group containing alkyl group, a benzyl group, a phenethyl group or a vinylmethyl group, X⁻ rep­resents an acid anion and n represents 1 or 2.

10. The combination of claim 2, wherein said back screen comprises a UV emitting phosphor having more than 80% of its spectral emission below 410 nm and its maximum of emission in the wavelength range of 300 - 360 nm.

11. The combination of claim 2, wherein said back screen comprises a UV emitting phosphor selected in the class consisting of lead or lanthanum activated barium sulfate phosphors, barium fluorohalide phosphors, lead activated barium silicate phosphors, gadolinium activated yttrium oxide phosphors, barium fluoride phosphors, and alkali metal activated rare earth niobate or tantalate phosphors.

12. The combination of claim 2, wherein said back screen comprises a UV emitting phosphor corresponding to the general formula
(Y_1-2/3x-1/3y, Sr_x, Li_y) TaO₄
wherein x and y are numbers such as to meet the condi­tions 10⁻⁵ ≦ x ≦ 1 and 10⁻⁴ ≦ y ≦ 0.1.

13. The combination of claim 2, wherein said back silver halide layer comprises chemically sensitized spec­trally insensitized silver bromoiodide grains.

14. A method for recording a radiation image com­prising the steps of (i) imagewise exposing to X radia­tions a combination of photosensitive elements comprising two separate front and back X-ray fluorescent screens and a silver halide radiographic element comprising a support base and front and back silver halide emulsion layers each coated on one surface of said support, wherein said front screen is arranged adjacent to said front silver halide layer and said back screen is arranged adjacent to said back silver halide layer, and wherein
1) said front screen comprises a first radiation emit­ting phosphor and said front silver halide layer comprises silver halide grains sensitive to said first radiation emitted by said front screen, and
2) said back screen comprises a second radiation emit­ting phosphor and said back silver halide layer com­prises silver halide grains sensitive to said second radiation emitted by said back screen,
and (ii) developing said silver halide radiographic ele­ment halide, characterized in that
a) said first radiation emitted by said front screen has a wavelength which differs from said second ra­diation emitted by said back screen by at least 50 nm,
b) said front silver halide emulsion layer is substan­tially insensitive to said second radiation emitted by said back screen, and
c) said back silver halide emulsion layer is substan­tially insensitive to said first radiation emitted by said front screen,
the difference in wavelength region of said first and second radiations and the insensitivity of each silver halide layer to radiation emitted by opposite screen be­ing such to reduce crossover exposure of at least 10 per­cent when compared with a symmetrical combination of a pair of green light emitting fluorescent screens and a double coated green sensitized silver halide radiograph­ic element.

15. The method for recording a radiation image ac­cording to claim 14, wherein

a) said front screen comprises a non-actinic radiation emitting phosphor and said front silver halide layer comprises silver halide grains spectrally sensitized to the radiation emitted by said front screen, and

b) said back screen comprises a UV emitting phosphor and said back silver halide layer comprises spec­trally insensitized silver halide grains.

16. The method for recording a radiation image ac­cording to claim 14, wherein said front screen comprises a green emitting phosphor having more than 80% of its spectral emission above 480 nm and its maximum of emis­sion in the wavelength range of 530 - 570 nm.

17. The method for recording a radiation image according to claim 14, wherein said front screen compris­es a green emitting phosphor represented by the general formula
(Ln_1-a-b, Tb_a, Tm_b)₂O₂S wherein Ln is at least one rare earth selected from lan­thanium, gadolinium and lutetium, and a and b are numbers such as to meet the conditions of 0.0005 ≦ a ≦ 0.09 and 0 ≦ b ≦ 0.01, respectively, or the general formula
(Y_1-c-a-b,Ln_c,Tb_a, Tm_b)₂O₂Tb
wherein Ln is at least one rare earth selected from lan­thanium, gadolinium and lutetium, and a, b and c are num­bers such as to meet the conditions of 0.0005 ≦ a ≦ 0.09, 0 ≦ b ≦ 0.01 and 0.65 ≦ c ≦ 0.95, respectively.

18. The method for recording a radiation image according to claim 14, wherein said front screen compris­es a terbium-activated gadolinium or lanthanium oxysul­phide phosphor having substantially emission peaks at 487 and 545 nm.

19. The method for recording a radiation image according to claim 14, wherein said front silver halide layer comprises silver halide grains spectrally sensi­tized with spectral sensitizing dyes of the cyanine or merocyanine dyes.

20. The method for recording a radiation image according to claim 14, wherein said front silver halide layer comprises silver halide grains spectrally sensi­tized with sensitizing dyes in such a way that it is sen­sitive for light in wavelength range of 530 - 570 nm.

21. The method for recording a radiation image according to claim 14, wherein said front silver halide emulsion layer comprises silver halide grains spectrally sensitized with sensitizing dyes represented by the gen­eral formula

wherein R₁₀ represents a hydrogen atom or an alkyl group, R₆, R₇, R₈ and R₉ each represent a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group, an amino group, an acylamino group, an acyloxy group, an alkoxycarbonyl group, an alkyl group, an alkoxycarbonyl­amino group or an aryl group, or, together, R₆ and R₇, and respectively R₈ and R₉ can be the atoms necessary to complete a benzene ring, R₁₁ and R₁₂ each represent an alkyl group, a hydroxyalkyl group, an acetoxyalkyl group, an alkoxyalkyl group, a carboxyl group containing alkyl group, a sulfo group containing alkyl group, a benzyl group, a phenethyl group or a vinylmethyl group, X⁻ rep­resents an acid anion and n represents 1 or 2.

22. The method for recording a radiation image according to claim 14, wherein said back screen comprises a UV emitting phosphor having more than 80% of its spec­tral emission below 410 nm and its maximum of emission in the wavelength range of 300 - 360 nm.

23. The method for recording a radiation image according to claim 14, wherein said back screen comprises a UV emitting phosphor selected in the class consisting of lead or lanthanum activated barium sulfate phosphors, barium fluorohalide phosphors, lead activated barium sil­icate phosphors, gadolinium activated yttrium oxide phosphors, barium fluoride phosphors, and alkali metal activated rare earth niobate or tantalate phosphors.

24. The method for recording a radiation image according to claim 14, wherein said back screen comprises a UV emitting phosphor corresponding to the general for­mula
(Y_1-2/3x-1/3y, Sr_y, Li_z) TaO₄
wherein x and y are numbers such as to meet the condi­tions 10⁻⁵ ≦ x ≦ 1 and 10⁻⁴ ≦ y ≦ 0.1.

25. The method for recording a radiation image according to claim 14, wherein said back silver halide layer comprises chemically sensitized spectrally insen­sitized silver bromoiodide grains.

26. A silver halide radiographic element compris­ing a support base and front and back silver halide emul­sion layers each coated on one surface of said support, characterized in that said front silver halide emulsion layer comprises silver halide grains sensitive to a wave­length region of the non-actinic radiation, and said back silver halide emulsion layer comprises UV or blue sen­sitive silver halide grains.

27. A combination of photosensitive elements for use in radiography comprising two separate front and back X-ray fluorescent screens and a silver halide radiograph­ic element comprising a support base and front and back silver halide emulsion layers each coated on one surface of said support, wherein said front screen is arranged adjacent to said front silver halide layer and said back screen is arranged adjacent to said back silver halide layer, and wherein
1) said front screen comprises a first radiation emit­ting phosphor and said front silver halide layer comprises silver halide grains sensitive to said first radiation emitted by said front screen, and
2) said back screen comprises a second radiation emit­ting phosphor and said back silver halide layer com­prises silver halide grains sensitive to said second radiation emitted by said back screen,
characterized in that
a) said first radiation emitted by said front screen has a wavelength which differs from said second radiation emitted by said back screen by at least 50 nm,
b) said front silver halide emulsion layer is substan­tially insensitive to said second radiation emitted by said back screen, and
c) said back silver halide emulsion layer is substan­tially insensitive to said first radiation emitted by said front screen,
the difference in wavelength region of said first and second radiations and the insensitivity of each silver halide layer to radiation emitted by opposite screen be­ing such to reduce crossover exposure of at least 10 per­cent when compared with a symmetrical combination of a pair of green light emitting fluorescent screens and a double coated green sensitized silver halide radiograph­ic element.

28. A combination of photosensitive elements for use in radiography comprising two separate front and back X-ray fluorescent screens and a silver halide radiograph­ic element comprising a support base and front and back silver halide emulsion layers each coated on one surface of said support, wherein said front screen is arranged adjacent to said front silver halide layer and said back screen is arranged adjacent to said back silver halide layer, and wherein
1) said front screen comprises a first radiation emit­ting phosphor and said front silver halide layer comprises silver halide grains sensitive to said first radiation emitted by said front screen, and
2) said back screen comprises a second radiation emit­ting phosphor and said back silver halide layer com­prises silver halide grains sensitive to said second radiation emitted by said back screen,
characterized in that

a) said first radiation emitted by said front screen is in a first wavelength region of the electromagnetic spectrum and said second radiation emitted by said back screen is in a second wavelength region of the electromagnetic spectrum,

b) said front silver halide emulsion layer is substan­tially insensitive to said second radiation emitted by said back screen, and

c) said back silver halide emulsion layer is substan­tially insensitive to said first radiation emitted by said front screen.

Drawing