AU623489B2

AU623489B2 - Radiographic elements with selected contrast relationships

Info

Publication number: AU623489B2
Application number: AU49329/90A
Authority: AU
Inventors: Phillip Carter Bunch; Robert Edward Dickerson
Original assignee: Eastman Kodak Co
Current assignee: Eastman Kodak Co
Priority date: 1989-02-23
Filing date: 1990-02-09
Publication date: 1992-05-14
Anticipated expiration: 2010-02-09
Also published as: BR9000888A; EP0384753A2; EP0384753A3; KR900013345A; JPH0328842A; CA2008456A1; JP2927489B2; AR243286A1; AU4932990A

Description

AUSTRALIA

Patents Act COMPLETE SPECIFICATIO 2 3 4 89

(ORIGINAL)

Class Int. Class Application Number: Lodged: Complete Specification Lodged: Accepted: Published: Priority 0009 o 0 00 a 00 0 0 0t door ti 001( Related Art: Applicant rs): Eastman Kodak Company 343 State Street, Rochester, New York, UNITED STATES OF AMERICA Address for Service is: PHILLIPS ORMONDE FITZPATRICK Patent and Trade Mark Attorneys 367 Collins Street Melbourne 3000 AUSTRALIA Complete Specification for the invention entitled: RADIOGRAPHIC ELEMENTS WITH SELECTED CONTRAST RELATIONSHIPS Our Ref 163233 POF Code: 122/4703 The following statement is a full description of this invention, including the best method of performing it known to applicant(s): 48t S 00 S0 0 1 6006 RADIOGRAPHIC ELEMENTS WITH SELECTED CONTRAST RELATIONSHIPS The invention relates to radiographic imaging. More specifically, the invention relates to double coated silver halide radiographic elements of the type employed in combination with intensifying screens.

In medical radiography an image of a patient's tissue and bone structure is produced by exposing the patient to X-radiation and recording the pattern of penetrating X-radiation using a radiographic element containing at least one 4) radiation-sensitive silver halide emulsion layer coated on a transparent (usually blue tinted) film 0 0 15 support. The X-radiation can be directly recorded by o 0 the emulsion layer where only limited areas of o 0 0 0 exposure are required, as in dental imaging and the 000. imaging of body extremities. However, a more efficient approach, which greatly reduces X-radiation exposures, is to employ an intensifying screen in 0.00 combination with the radiographic element. The 0 0 intensifying screen absorbs X-radiation and emits 0. 0 longer wavelength electromagnetic radiation which silver halide emulsions more readily absorb. Another 0. 0 00 0 25 technique for reducing patient exposure is to coat two silver halide emulsion layers on opposite sides of the film support to form a "double coated" radiographic 060 0element.

Diagnostic needs can be satisfied at the lowest patient X-radiation exposure levels by employing a double coated radiographic element in combination with a pair of intensifying screens. The silver halide emulsion layer unit on each side of the support directly absorbs about 1 to 2 percent of incident X-radiation. The front screen, the screen nearest the X-radiation source, absorbs a much higher percentage of X-radiation, but still transmits -2sufficient X-radiation to expose the back screen, the screen farthest from the X-radiation source. In the overwhelming majority of applications the front and back screens are balanced so that each absorbs about the same proportion of the total X-radiation.

However, a few variations have been reported from time to time. A specific example of balancing front and back screens to maximize image sharpness is provided by Luckey et al U.S. Patent 4,710,637. Lyons et al U.S. Patent 4,707,435 discloses in Example 10 the combination of two proprietary screens, Trimax 2

TM

employed as a front screen and Trimax 12FTM employed 0000 0o Q as a back screen. K. Rossman and G. Sanderson, 00 o "Validity of the Modulation Transfer Function of 00o°o 15 Radiographic Screen-Film Systems Measured by the Slit °OeG Method", Phys. Med. iiol., 1968, vol. 13, no. 2, pp.

ooe 0259-268, report the use of unsymmetrical screen-film 0o assemblies in which either the two screens had measurably different optical characteristics or the two emulsions had measurably different optical properties.

An imagewise exposed double coated radiographic element contains a latent image in each of the two silver halide emulsion units on opposite 9 1 25 sides of the film support. Processing converts the latent images to silver images and concurrently fixes 0000out undeveloped silver halide, rendering the film 0 0 oo light insensitive. When the film is mounted on a view box, the two superimposed silver images on opposite sides of the support are seen as a single image against a white, illuminated background.

It has been a continuing objective of medical radiography to maximize the information content of the diagnostic image while minimizing patient exposure to X-radiation. In 1918 the Eastman Kodak Company introduced the first medical radiographic product that was double coated, and the Patterson Screen Company 1- that same year introduced a matched intensifying screen pair for that product.

An art recognized difficulty with employing double coated radiographic elements in combination with intensifying screens as described above is that some light emitted by each screen passes through the transparent film support to expose the silver halide emulsion layer unit on the opposite side of the support to light. The light emitted by a screen that exposes the emulsion layer unit on the opposite side of the support reduces image sharpness. The effect is referred to in the art as crossover.

00 o A variety of approaches have been suggested '00 0 0 0° to reduce crossover, as illustrated by Research 00 00 0 oe 15 Disclosure, Vol. 184, August 1979, Item 18431, Section 0oo~o, V. Cross-Over Exposure Control. Research Disclosure 000 is published by Kenneth Mason Publications, Ltd., 0 0 Dudley Annex, 21a North Street, Emsworth, Hampshire P010 7DQ, England. While some of these approaches are capable of entirely eliminating crossover, they either interfere with (typically entirely prevent) concurrent viewing of the superimposed silver images on opposite sides of the support as a single image, require 4 separation and tedious manual reregistration of the silver images in the course of eliminating the crossover reduction medium, or significantly .o desensitize the silver halide emulsion. As a result, o none of these crossover reduction approaches have come into common usage in the radiographic art. An example of a recent crossover cure teaching of this type is Bollen et al European published patent application 276,497, which interposes a reflective support between the emulsion layer units during imaging.

The most successful approach to crossover reduction yet realized by the art consistent with viewing the superimposed silver images through a transparent film support without manual registration ~L

I

-4of images has been to employ double coated radiographic elements containing spectrally sensitized high aspect ratio tabular grain emulsions or thin intermediate aspect ratio tabular grain emulsions, illustrated by Abbott et al U.S. Patents 4,425,425 and 4,425,426, respectively. Whereas radiographic elements typically exhibited crossover levels of at least 25 percent prior to Abbott et al, Abbott et al provide examples of crossover reductions in the 15 to 22 percent range.

Still more recently Dickerson et al U.S.

Patent 4,803,150 has demonstrated that by combining o othe teachings of Abbott et al with a processing 0. o solution decolorizable microcrystalline dye located :0o0 0 15 between at least one of the emulsion layer units and 0 the transparent film support "zero" crossover levels 0 can be realized. Since the technique used to 000 000 determine crossover, single screen exposure of a double coated radiographic element, cannot distinguish between exposure of the emulsion layer unit on the side of the support remote from the screen caused by crossover and the exposure caused by direct absorption of X-radiation, "zero" crossover radiographic elements in reality embrace radiographic elements with a 44 measured crossover (including direct X-ray absorption) of less than about 5 percent. Specific selections of hydrophilic colloid coating coverages in the emulsion 00 0 00 o and dye containing layers to allow the "zero" I crossover radiographic elements to emerge dry to the touch from a conventional rapid access processor in less than 90 seconds with the crossover reducing microcrystalline dye decolorized.

Although major improvements in radiographic elements have occurred over the years, some limitations have been heretofore accepted as being inherent consequences of the complexities of medical diagnostic imaging. Medical diagnostic imaging places LI -Ji _LI_ L. I I extreme and varying demands on radiographic elements.

One of the most difficult demands can be illustrated by the chest X-ray. In a typical chest X-ray the radiologist is confronted with attempting to visually detect both lung and heart anomalies, even though the X-radiation absorption in the heart area is about times greater than that of the lung area. Most double coated radiographic elements when exposed to provide an optimum contrast image of the lungs provide no visually discernable contrast in the image of the heart. This is because the radiographic element is receiving in the heart area only about one tenth the o exposure it is receiving in the lung area. The art o o has prior to this invention attempted to meet the 0o0 15 needs of radiologists for chest X-ray images providing visually discernable features in both the heart and o °o °lung image areas by providing extended latitude o4 radiographic elements. Extended latitude radiographic elements are typically created by employing polydispersed silver halide emulsions to provide lower average contrasts and therefore a wider range of 0000exposures separating minimum and maximum density 4 exposures.

It is an object of this invention to provide radiographic elements capable of increasing the information content of an image of a subject exhibiting wide ranging differences in its X-ray 000 0. absorption densities.

In one aspect this invention is directed to a radiographic element comprised of a transparent film support, first and second silver halide emulsion layer units coated on opposite sides of the film support, and means for reducing to less than 10 percent crossover of electromagnetic radiation of wavelengths longer than 300 nm capable of forming a latent image in the silver halide emulsion layer units, said crossover reducing means being decolorized in less than 90 seconds during processing of said emulsion layer units.

The radiographic elements are characterized in that the first and second silver halide emulsion layer units each contain a spectral sensitizing dye, the crossover reducing means is comprised of a hydrophilic colloid layer interposed between at least one of said silver halide emulsion layer units and said support contdining a particulate dye capable of absorbing electromagnetic radiation to which said silver halide emulsion layer unit on the opposite side of the support is responsive.

The first silver halide emulsion layer unit exhibits an average contrast of less than 2.0, based on density measurements at 0.25 and 2.0 above minimum density and the second silver halide emulsion layer unit exhibits an average cortrast of at lz&t 2.5, based on density measurements at 0.25 and 2.0 above minimum density, The contrast of the first silver halide emulsion layer unit is determined with the first o silver halide emulsion unit replacing the second silver halide o° emulsion unit to provide an arrangement with the first silver halide emulsion unit present on both sides of the transparent support, and the contrast of the second silver halide emulsion layer unit is determined with the second silver halide :°000 enulsion unit replacing the first silver halide emulsion unit '0:0o to provide an arrangement with the second silver halide emulsion layer unit present on both sides of the transparent support.

It has been discovered that these double coated radiographic elements are capable of yielding a greater than percent increase in contrast in heart areas while providing the same contrast in lung areas as conventional extended latitude double coated radiographic elements. The invention therefore represents a significant advance in meeting the diagnostic needs of medical radiologists. Further, while the advantages are discussed in terms of simultaneously obtaining visually useful imaging detail in both heart and lung areas, it is appreciated that the advantages of the invention extend to any imaging application in which the X-radiation absorption capabilities of the object being examined differ over a wide *4 e*A range.

ri L il ii I o 00 0 00 01* 00 a a 0 0 0 0 a a 00 0 00 V0 0 0 020Q -7- Brief Description of the Drawings Figure 1 is a schematic diagram of an assembly consisting of a double coated radiographic element sandwiched between two intensifying screens.

The double coated radiographic elements of this invention offer the capability of producing superimposed silver images capable of transmission viewing which can satisfy the highest standards of the art in terms of speed and sharpness. At the same time the radiographic elements are capable of providing useful imaging detail over a wide range of exposure levels within a single image.

This is achieved by constructing the radiographic element with a transparent film support 15 and first and second emulsion layer units coated on opposite sides of the support. This allows transmission viewing of the silver images on opposite sides of the support after exposure and processing.

Between the emulsion layer units on opposite sides of the support, means are provided for reducing to lesL than 10 percent crossover of electromagnetic radiation of wavelengths longer than 300 nm capable of forming a latent image in the silver halide emulsion layer units. In addition to having the capability of absorbing longer wavelength radiation during imagewise exposure of the emulsion layer units the crossover reducing means must also have the capability of being decolorized in less than 90 seconds during processing, so that no visual hindrance is presented to viewing the superimposed silver images.

The crossover reducing means reduces crossover to less than 10 percent, preferably reduces crossover to less than 5 percent, and optimally reduces crossover to less than 3 percent. However, it must be kept in mind that for crossover measurement convenience the crossover percent being referred to also includes "false crossover", apparent crossover 0*00 0600 0000 .00.0 0 00 0o 0 o Co.t.

0 9 0. 0 ~L crl o? 0 0 00 o Q 0 0 4 a0 4 04 4 0 4 4 0 04 I 0 O d 0. 0 that is actually the product of direct X-radiation absorption. That is, even when crossover of longer wavelength radiation is entirely eliminated, measured crossover will still be in the range of 1 to 2 percent, attributable to the X-radiation that is directly absorbed by the emulsion farthest from the intensifying screen. Crossover percentages are determined by the procedures set forth in Abbott et al U.S. Patents 4,425,425 and 4,425,426.

In addition to the above requirements, the radiographic elements of this invention differ from conventional double coated radiographic elements in requiring that the first and second emulsion layer units exhibit significantly different average 15 contrasts. The first silver halide emulsion layer unit exhibits an average contrast of less than while the second silver halide emulsion layer unit exhibits an average contrast of at least 2.5. It is preferred that the average contrasts of the first and second silver halide emulsion layer units differ by at least 1.0. While the best choice of average differences between the first and second emulsion layer units can differ widely, depending up the the application to be served, in most instances the first 25 and second emulsion layer units exhibit an average contrast difference in the range of from 0.5 to optimally from 1.0 to The first and second silver halide emulsion units can exhibit identical or differing speeds.

However, since the lower average contrast emulsion layer unit is normally relied upon to provide image detail in areas receiving the least ezposure to X-radiation, it is preferred that the lower average contrast emulsion unit exhibit a speed which is at least equal to that of the higher average contrast emulsion layer unit. The lower average contrast emulsion layer unit can exhibit speeds up to 10 times L. ~u~Y- PP 9 00 U Op 0 ps 00 4 c 49 pp.

-9greater than those of the higher average contrast emulsion layer unit. It is generally preferred that lower average contrast emulsion layer unit exhibit a speed ranging from equal to to four times greater than that of the higher average contrast emulsion layer unit.

Customarily sensitometric characterizations of double coated radiographic elements generate characteristic (density vs. log exposure) curves that are the product of two identical emulsion layer units, one coated on each of the two sides of the transparent support. Therefore, to keep contrast and other sensitometric measurements (minimum density, speed, maximum density, etc.) as compatible with customary 15 practices as possible, the contrast and other sensitometric characteristics of the first silver halide emulsion layer unit are determined with the first silver halide emulsion unit replacing the second silver halide emulsion unit to provide an arrangement with the first silver halide emulsion unit present on both sides of the tranparent support. The contrast and other sensitometric characteristics of the second silver halide emulsion layer unit are similarly determined with the second silver halide emulsion unit replacing the first silver halide emulsion unit to provide an arrangement with the second silver halide emulsion unit present on both sides of the tranparent support.

As employed herein the term "average contrast" is employed to indicate a contrast determined by reference to an emulsion layer unit characteristic curve at a density of 0.25 above minimum density and at a density of 2.0 above minimum density. The average contrast is the density difference, 1.75, divided by the log of the difference in exposure levels at two reference points on the characteristic curve, where the exposure levels are O r 0 41 4 4r 00 0

-A

0o 0 o 0 00 o 0 0 00 0 0 0000 0 coo 0 0 0 0000 0 So o a a o 0 4 0060 0 00 0 0 0 meter-candle-seconds. As herein employed all references to photographic speed are understood to refer to comparisons of exposure levels at a reference density of 1.0 above minimum density. While the speed and average contrast characteristic curve reference points have been arbitrarily selected, the selections are typical of those employed in the art. For nontypical characteristic curves direct positive imaging or unusual curve shapes) other reference densities can be selected.

By reducing or eliminating crossover and employing emulsion layer units differing in average contrast and, optionally, speed, independent radiographic records are formed in a single double 15 coated radiographic element that provide better definition of exposure differences in areas differing in their level of exposure by 10 times (1.0 log E, where E is measured in meter-candle-seconds). A difference of 1.0 log E is also referred to herein as difference of 100 relative log exposure units. For example, a speed difference of 0.3 log E is a speed difference of 30 log relative exposure units, with one emulsion layer unit exhibiting a speed twice that of the other.

The remaining features of the double coated radiographic elements of this invention can take any convenient conventional form. In a specifically preferred form of the invention the advantages of (1) tabular grain emulsions as disclosed by Abbott et al U.S. Patents 4,425,425 and 4,425,426, cited above, hereinafter referred to as T-Grain T M emulsions; (2) sharpness levels attributable to crossover levels of less than 10 percent, crossover reduction without emulsion desensitization or residual stain, and (4) the capability of rapid access processing, are realized in addition to the advantages discussed above.

j Ci

II

I

-11- These additional advantages can be realized by selecting the features of the double coated radiographic element of this invention according to the teachings of Dickerson et al U.S. Patent 4,803,150. The following represents a specific preferred selection of features. Referring to Figure 1, in the assembly shown a radiographic element 100 according to this invention is positioned between a pair of light emitting intensifying screens 201 and 202. The radiographic element support is comprised of a transparent radiographic support element 101, typically blue tinted, capable of transmitting light o O to which it is exposed and optionally, similarly transmissive subbing units 103 and 105. On the first o o 0 S 15 and second opposed major faces 107 and 109 of the 0 o support formed by the under layer units are crossover reducing hydrophilic colloid layers 111 and 113, respectively. Overlying the crossover reducing layers 111 and 113 are light recording latent image forming silver halide emulsion layer units 115 and 117, respectively. Each of the emulsion layer units is ot°c formed of one or more hydrophilic colloid layers including at least one silver halide emulsion layer.

Overlying the emulsion layer units 115 and 117 are optional hydrophilic colloid protective overcoat layers 119 and 121, respectively. All of the hydrophilic colloid layers are permeable to processing o0.l osolutions.

In use, the assembly is imagewise exposed to X-radiation. The X-radiation is principally absorbed by the intensifying screens 201 and 202, which promptly emit light as a direct function of X-ray exposure. Considering first the light emitted by screen 201, the light recording latent image forming emulsion layer unit 115 is positioned adjacent this screen to receive the light which it emits. Because of the proximity of the screen 201 to the emulsion 00 0 0 00o aOo 00 0 0 oo Oa 00 00 4 o 4 40;; 0 4 4 49 900 4 -12layer unit 115 only minimal light scattering occurs before latent image forming absorption occurs in this layer unit. Hence light emission from screen 201 forms a sharp image in emulsion layer unit 115.

However, not all of the light emitted by screen 201 is absorbed within emulsion layer unit 115. This remaining light, unless otherwise absorbed, will reach the remote emulsion layer unit 117, resulting in a highly unsharp image being formed in this remote emulsion layer unit. Both crossover reducing layers 111 and 113 are interposed between the screen 201 and the remote emulsion layer unit and are capable of intercepting and attenuating this remaining light. Both of these layers thereby contribute to reducing crossover exposure of emulsion layer unit 117 by the screen 201. In an exactly analogous manner the screen 202 produrs a sharp image in emulsion layer unit 117, and the light absorbing layers 111 and 113 similarly reduce crossover exposure of the emulsion layer unit 115 by the screen 202.

Following exposure to produce a stored latent image, the radiographic element 100 is removed from association with the intensifying screens 210 and 202 and processed in a rapid access processor-that is, a

TM

25 processor, such as an RP-X-Omat TM processor, which is capable of producing a image bearing radiographic element dry to the touch in less than 90 seconds.

Rapid access processors are illustrated by Barnes et al U.S. Patent 3,545,971 and Akio et al published European published patent application 248,390.

Since rapid access processors employed commercially vary in their specific processing cycles and selections of processing solutions, the preferred radiographic elements satisfying the requirements of the present invention are specifically identified as being those that are capable of emerging dry to the touch when processed in 90 seconds according to the L I- na-- I r -13following reference conditions: development 24 seconds at 35 0

C,

fixing 20 seconds at 35 0

C,

washing 10 seconds at 35 0 C, and drying 20 seconds at 65 0

C,

where the remaining time is taken up in transport between processing steps. The development step employs the following developer: Hydroquinone 30 g l-Phenyl-3-pyrazolidone 1.5 g KOH 21 g NaHCO 3 7.5 g

K

2 SOg 44.2 g o Na 2

S

2 0 5 12.6 g NaBr 35 g o 5-Methylbenzotriazole 0.06g 0 0 Glutaraldehyde 4.9 g 0000 Water to 1 liter at pH 10.0, and the fixing step employs the following fixing composition: Ammonium thiosulfate, 60% 260.0 g o o Sodium bisulfite 180.0 g o a Boric acid 25.0 g Acetic acid 10.0 g 0 0, 25 Aluminum sulfate 8.0 g Water to 1 liter at pH 3.9 to The preferred radiographic elements of the o 00: present invention make possible the unique combination of advantages set forth above by employing (1) substantially optimally spectrally sensitized tabular grain emulsions in the emulsion layer units to reach low crossover levels while achieving the high covering power and other known advantages of tabular grain emulsions, one or more particulate dyes in the interlayer units to further reduce crossover to less than 10 percent without emulsion desensitization and minimal or no residual dye stain, and hydrophilic -14colloid swell and coverage levels compatible with obtaining uniform coatings, rapid access processing, and reduced or eliminated wet pressure sensitivity.

Each of these features of the invention is discussed in more detail below: Each uWer layer unit contains a processing solution fydrophilic colloid and a particulate dye, The total concentration of the microcrystalline dye in both under layer units is sufficient to reduce the i0 crossover of the radiographic element below percent. This can be achieved when the concentration of the dye is chosen to impart to the structure separating the emulsion layer units an optical density of at least 2.00 at the peak wavelength of screen o 15 emission to which the emulsion layer units are responsive. Although the dye can be unequally o o distributed between the two under layer units, it is oo preferred that each under layer unit contain sufficient dye to raise the optical density of that under layer unit to 1.00. Using the latter value as a point of reference, since it is conventional practice to employ intensifying screen-radiographic element combinations in which the peak emulsion sensitivity matches the peak light emission by the intensifying screens, it follows that the dye also exhibits a density of at least 1.00 at the wavelength of peak emission of the intensifying screen. Since neither screen emissions nor emulsion sensitivities are &1 t confined to a single wavelength, it is preferred to 30 choose particulate dyes, including combinations of particulate dyes, capable of imparting a density of 1.00 or more over the entire spectral region of significant sensitivity and emission. For radiographic elements to be used with blue emitting intensifying screens, such as those which employ calcium tungstate or thulium activated lanthanum oxybromide phosphors, it is generally preferred that

T-

0 0 Oann 0 0 o oo 04 00 0004 0000 S000 09o the particulate dye be selected to produce an optical density of at least 1.00 over the entire spectral region of 400 to 500 nm. For radiographic elements intended to be used with green emitting intensifying screens, such as those employing rare earth terbium) activated gadolinium oxysulfide or oxyhalide phosphors, it is preferred that the particulate dye exhibit a density of at least 1.00 over the spectral region of 450 to 550 nm. To the extent the wavelength of emission of the screens or the sensitivities of the emulsion layers are restricted, the spectral region over which the particulate dye must also effectively absorb light is correspondingly reduced.

While particulate dye optical densities of 15 1.00, chosen as described above, are effective to reduce crossover to less than 10 percent, it is specifically recognized that particulate dye densities can be increased until radiographic element crossover is effectively eliminated. For example, by increasing the particulate dye concentration so that it imparts a density of 2.0 to the radiographic element, crossover is reduced to only 1 percent.

Since there is a direct relationship between the dye concentration and the optical density produced 25 for a given dye or dye combination, precise optical density selections can be achieved by routine selection procedures. Because dyes vary widely in their extinction coefficients and absorption profiles, it is recognized that the weight or even molar concentrations of particulate dyes will vary from one dye or dye combination selection to the next.

The size of the dye particles is chosen to facilitate coating and rapid decolorization of the dye. In general smaller dye particles lend themselves to more uniform coatings and more rapid decolorization. The dye particles employed in all instances have a mean diameter of less than 10.0 pm and

I.

o II 0 00 ~L i d -16- 04 0 0o 0 0o 0 0 0 o o q00 0000 preferably less than 1.0 pm. There is no theoretical limit on the minimum sizes the dye particles can take. The dye particles can be most conveniently formed by crystallization from solution in sizes ranging down to about 0.01 pm or less.

Where t'.e dyes are initially crystallized in the form of particles larger than desired for use, conventional techniques for achieving smaller particle sizes can be employed, such as ball milling, roller milling, sand milling, and the like.

An important criterion in dye selection is their ability to remain in particulate form in hydrophilic colloid layers of radiographic elements.

While the hydrophilic colloids can take any of various 15 conventional forms, such as any of the forms set forth in Research Disclosure, Vol. 176, December 1978, Item 17643, Section IX, Vehicles and vehicle extenders, the hydrophilic colloid layers are most commonly gelatin and gelatin derivatives acetylated or phthalated gelatin). To achieve adequate coating uniformity the hydiophilic colloid must be coated at a 2 layer coverage of at least 10 mg/dm2. Any convenient higher coating coverage can be employed, provided the total hydrophilic colloid coverage per side of the radiographic element does not exceed that compatible with rapid access processing. Hydrophilic colloids are typically coated as aqueous solutions in the pH range of from about 5 to 6, most typically from to 6.0, to form radiographic element layers. The dyes which are selected for use in the practice of this invention are those which are capable of remaining in particulate form at those pH levels in aqueous solutions.

Dyes which by reason of their chromophoric make up are inherently ionic, such as cyanine dyes, as well as dyes which contain substituents which are ionically dissociated in the above-noted pH ranges of 1441 I 4 f I i4t St c-ulr -17coating may in individual instances be sufficiently insoluble to satisfy the requirements of this I inventioi, but do not in general constitute preferred classes of dyes for use in the practice of the invention. For example, dyes with sulfonic acid substituents are normally too soluble to satisfy the requirements of the invention. On the other hand, nonionic dyes with carboxylic acid groups (depending in some instances on the specific substitution location of the carboxylic acid group) are in general insoluble under aqueous acid coating conditions.

Specific dye selections can be made from known dye 000 characteristics or by observing solubilities in the pH 1o 0 range of from 5.5 to 6.0 at normal layer coating 0 0 0 0 °o 15 temperatures-e.g., at a reference temperature of 40 0

C.

00 Preferred particulate dyes are nonionic polymethine dyes, which include the merocyanine, 0 0 oo.. oxonol, hemioxonol, styryl, and arylidene dyes.

o The merocyanine dyes include, joined by a methine linkage, at least one basic heterocyclic nucleus and at least one acidic nucleus. The nuclei can be joined by an even number or methine groups or in so-called "zero methine" merocyanine dyes, the methine linkage takes the form of a double bond between methine groups incorporated in the nuclei.

Basic nuclei, such as azolium or azinium nuclei, for example, include those derived from pyridinium, 0*oo quinolinium, isoquinolinium, oxazolium, pyrazolium, pyrrolium, indolium, oxadiazolium, 3H- or 1H-benzoindolium, pyrrolopyridinium, phenanthrothiazolium, and acenaphthothiazolium quaternary salts.

Exemplary of the basic heterocyclic nuclei are those satisfying Formulae I and II.

(I)

3 I- q _I III-^-SI~~CI -18-

(II)

Q1- -C=L-(L=-L)i7N-R where Z3 represents the elements needed to complete a cyclic nucleus derived from basic heterocyclic nitrogen compounds such as oxazoline, oxazole, benzoxazole, the naphthoxazoles naphth[2,1-d]oxazole, naphth[2,3-d]oxazole, and naphth[1,2-dloxazole), oxadiazole, 2- or 4-pyridine, 2- or 4-quinoline, 1- or 3-isoquinoline, benzoquinoline, 1H- or 3H-benzoindole, and pyrazole, which nuclei may be substituted on the ring by one or more 0000 0 of a wide variety of substituents such as hydroxy, the 00 0 O0 O 15 halogens fluoro, chloro, bromo, and iodo), :"000 alkyl groups or substituted alkyl groups 0 0 methyl, ethyl, propyl, isopropyl, butyl, octyl, dodecyl, octadecyl, 2-hydroxyethyl, 2-cyanoethyl, and trifluoromethyl), aryl groups or substituted aryl groups phenyl, l-naphthyl, 2-naphthyl, 3-carboxyphenyl, and 4-biphenylyl), aralkyl groups benzyl and phenethyl), alkoxy groups methoxy, ethoxy, and isopropoxy), aryloxy groups phenoxy and l-naphthoxy), alkylthio groups methylthio and ethylthio), arylthio groups phenylthio, p-tolylthio, and 2-naphthylthio), methylenedioxy, cyano, 2-thienyl, styryl, amino or 000substituted amino groups anilino, dimethylamino, diethylamino, and morpholino), acyl groups, formyl, acetyl, benzoyl, and benzenesulfonyl); Q' represents the elements needed to complete a cyclic nucleus derived from basic heterocyclic nitrogen compounds such as pyrrole, pyrazole, indazole, and pyrrolopyridine; R represents alkyl groups, aryl groups, alkenyl groups, or aralkyl groups, with or without substituents, carboxy, hydroxy, sulfo, alkoxy, ~c I -19sulfato, thiosulfato, phosphono, chloro, and bromo substituents); L is in each occurrence independently selected to represent a substituted or unsubstituted methine 8 8 group-e.g., -CR 8 groups, where R represents hydrogen when the methine group is unsubstituted and most commonly represents alkyl of from 1 to 4 carbon atoms or phenyl when the methine group is substituted; and q is 0 or i.

Merocyanine dyes link one of the basic heterocyclic nuclei described above to an acidic keto methylene nucleus through a methine linkage, where the 8 o o methine groups can take the form -CR described 0 15 above. The greater the number of the methine groups i linking nuclei in the polymethine dyes in general and the merocyanine dyes in particular the longer the absorption wavelengths of the dyes.

Merocyanine dyes link one of the basic heterocyclic nuclei described above to an acidic keto methylene nucleus through a methine linkage as described above. Exemplary acidic nuclei are those which satisfy Formula III.

S'

(III)

"1 25 0 SU -G 1 \G2

G

So owhere G represents an alkyl group or substituted alkyl group, an aryl or substituted aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a hydroxy group, an amino group, or a substituted amino group, wherein exemplary substituents can take the various forms noted in connection with Formulae VI and

VII;

G

2 can represent any one of the groups listed for G 1 and in addition can represent a cyano group, L o s, C

C

C C C

CC

cO C V o e C C 0 o o C

C

CC',

S S an alkyl, or arylsulfonyl group, or a group represented by -C-G or Gtaken together withGca represent the elements needed to complete a cyclic acidic nucleus such as those derived from 2,4-oxazolidinone 3-ethyl-2,4--oxazolidindione), 2,4-thiazolidindione 3-methyl--2,4-thiazolidindione), 2-thio-2,4-oxazolidindione 3-phenyl-2thio-2,4-oxazolidindione), rhodanine, such as 3-ethyirhodanine, 3-phenyirhodanine, 3-(3-dimethylaminopropyl)rhodaiiine, and 3-carboxymethylrhodanine, hydantoin l,3-diethylhydantoin and 3-ethyl-lphenylhydantoin), 2-thiohydantoin 1--ethyl-3- 15 phenyl-2-thiohydantoin, 3-heptyl-l-phenyl-2-thiohydantomn, and arylsulfonyl-2--thiohydantoin), 2-pyrazolin- 5-one, such as 3-methyl--l-phenyl-2-pyrazolin-5-one and 3-methyl-l-(4-carboxyphenyl)-2-pyrazolin-5-one, 3-phenyl-2-isoxazolin-5one), 3,5-pyrazolidindione l,2-diethyl-3,5pyrazolidindione and 1, 2-diphenyl-3 ,5-pyrazolid indione), 1,3-indandione, l,3-dioxane-4,6-dione, 1,3-cyclohexanedione, barbituric acid 1-ethylbarbituric acid and 1,3-diethylbarbituric acid), and 2-thiobarbituric acid 1,3-diethyl- 2-thiobarbituric acid and l,3-bis(2-methoxyethyl)-2thiobarbituric acid).

Useful hemioxonol dyes exhibit a keto methylene nucleus as shown in Formula III and a nucleus as shown in Formula IV.

(IV)

G3 where G 3and G4may be the same or different and may represent alkyl, substituted alkyl, aryl, substituted 11___1_ -21aryl, or aralkyl, as illustrated for R ring 3 4 substituents in Formula I or G and G taken together complete a ring system derived from a cyclic secondary amine, such as pyrrolidine, 3-pyrroline, piperidine, piperazine 4-methylpiperazine and 4-phenylpiperaine), morpholine, 1,2,3,4-tetrahydroquinoline, decahydroquinoline, 3-azabicyclo[3,2,2]nonane, indoline, azetidine, and hexahydroazepine.

Exemplary oxonol dyes exhibit two keto methylene nuclei as shown in Formula III joined through one or higher uneven number of methine groups.

Useful arylidene dyes exhibit a keto methylene nucleus as shown in Formula III and a Y a nucleus as shown in Formula V joined by a methine oa o 15 linkage as described above containing one or a higher o uneven number of methine groups.

o,,o (V) o 0 O*0 0

G

where

SG

3 and G 4 are as previously defined.

A specifically preferred class of oxonol dyes for use in the practice of the invention are the oxonol dyes disclosed in Factor and Diehl European Spublished patent application 299,435. These oxonol dyes satisfy Formula VI.

S4. (VI) 0 OH U

I

HO C-u R1 2

HO

2 C-K ^jV( =CH-CH=CH- <,-COH,

R

wherein 1 2 R and R each independently represent alkyl of from 1 to 5 carbon atoms.

I I -A -22- A specifically preferred class of arylidene dyes for use in the practice of the invention are the arylidene dyes disclosed in Diehl and Factor European published patent applications 274,723 and 2,94,461.

These arylidene dyes satisfy Formula VII.

(VII)

R

-I

0=

-R

wherein S0000 o 0 o o o o 0 0 0 oo 0 o o o 00 0 0400 0004 A represents a substituted or unsubstituted acidic nucleus having a carboxyphenyl or sulfonamido- phenyl substituent selected from the group consisting of 2-pryazolin-5-ones free of any substituent bonded 15 thereto through a carboxyl group, rhodanines; hydantoins; 2-thiohydantoins; 4-thiohydantoins; 2,4-oxazolidindiones; 2-thio-2,4-oxazolidindiones; isoxazolinones; barbiturics; 2-thiobarbiturics and indandiones; R represents hydrogen, alkyl of 1 to 4 carbon atoms or benzyl; R and R 2 each independently, represents alkyl or aryl; or taken together with R 5

R

6

N,

and the carbon atoms to which they are attached represent the atoms needed to complete a julolidene ring; 3 R represents H, alkyl or aryl; R and R each independently, represents H or

R

5 taken together with R or R 6 taken together with R 2 each may represent the atoms necessary to complete a 5 or 6 membered ring; and m is 0 or 1.

Oxazole and oxazoline pyrazolone merocyanine particulate dyes are also contemplated. The particulate dyes of Formula VIII are presentative.

0 0 0 06 0 ~*rra~a~ l--~llarmar~-- -i -23-

(VIII)

0 R lx >O XUN R R! .=4CH-CH^= R/ \N11>R4 R7 In formula R 1 and R 2 are each independently substituted or unsubstituted alkyl or substituted or unsubstituted aryl, or together represent the atoms necessary to complete a substituted or unsubstituted 5- or 6-membered ring.

R

3 and R 4 each independently represents H, o substituted or unsubstituted alkyl, substituted or o 15 unsubstituted aryl, CO 2 H, or NHS0 2

R

6

R

5 is H, substituted or unsubstituted alkyl, substituted or Sunsubstituted aryl, carboxylate COOR where R o is substituted or unsubstituted alkyl), or substituted or L._substituted acyl, R 6 and R 7 are each independently substituted or unsubstituted alkyl or substituted or unsubstituted aryl, and n is 1 or 2. R 8 is either substituted or unsubstituted alkyl, or is part of a double bond between the ring carbon atoms to which R 1 and R 2 are attached. At least one of the aryl rings of the dye molecule must have at least one substituent that is CO2H or

NHSO

2

R

6 Oxazole and oxazoline benzoylacetonitrile merocyanine particulate dyes are also contemplated.

The particulate dyes of Formula IX are representative.

I

R 0 Rl\ /0

C-

S*=CH-CH=C

KN

7 R N1 CN 2 I

I

R

IP

-24- In Formula IX, R 1

R

2

R

3

R

4

R

5 and R 6 may each be substituted or unsubstituted alkyl or substituted or unsubctituted aryl, preferably substituted or unsubstituted alkyl of 1 to 6 carbon atoms or substituted or unsubstituted aryl of 6 to 12 carbon atoms. R 7 may be substituted or unsubstituted alkyl of from 1 to 6 carbon atoms. The alkyl or aryl groups may be substituted with any of a number of substituents as is known in the art, other than those, such as sulfo substituents, that would tend to increase the solubility of the dye so much as to cause it to become soluble at coating pH's.

Examples of useful substituents include halogen, alkoxy, ester groups, amido, acyl, and alkylamino.

So 15 Examples of alkyl groups include methyl, ethyl, S°"oa n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, P oo n-hexyl, or isohexyl. Examples of aryl groups include phenyl, naphthyl, anthracenyl, pyridyl, and 0 o styryl.

R

1 and R 2 may also together represent the atoms necessary to complete a substituted or unsubstituted 5- or 6-membered ring, such as phenyl, naphthyl, pyridyl, cyclohexyl, dihydronaphthyl, or acenaphthyl. This ring may be substituted with substituents, other than those, such as sulfo substituents, that would tend to increase the solubility of the dye so much as to cause it to become soluble at coating pH's. Examples of useful Ssubstituents include halogen, alkyl, alkoxy, ester, amido, acyl, and alkylamino.

Useful bleachable particulate dyes can be found among a wide range of cyanine, merocyanine, oxonol, arylidene merostyryl), anthraquinone, triphenylmethine, azo, azomethine, and other dyes, such as those satisfying the criteria of Formula X.

(X)

n y n I -111_1--_1^111 where D is a chromophoric light-absorbing compound, which may or may not comprise an aromatic ring if y is not 0 and which comprises an aromatic ring if y is 0, A is an aromatic ring bonded directly or indirectly to X is a substituent, either on A or on an aromatic ring portion of D, with an ionizable proton, y is 0 to and n is 1 to 7, where the dye is substantially aqueous insoluble at a pH of 6 or below and substantially aqueous soluble at a pH of 8 or above.

Synthesis of the particulate dyes can be achieved by procedures known in the art for the synthesis of dyes of the same classes. For example, 00ooo00 "a those familiar with _chniques for dye synthesis 0 15 disclosed in "The Cyanine Dye' 1' Related Soo Compounds", Frances Hamer, Interscience Publishers, 0 0 1964, could readily synthesize the cyanine, 0.00 merocyanine, merostyryl, and other polymethine dyes.

The oxonol, anthraquinone, triphenylmethane, azo, and azomethine dyes are either known dyes or substituent variants of known dyes of these classes and can be synthesized by known or obvious variants of known i synthetic techniques forming dyes of these classes.

Examples of particulate bleachable dyes useful in the practice of this invention include the following: 0 0 -26- Table I Trimethine Pyrazolone Ginnamylidene Dyes General Structure: C7 z =CH-CH~i CH 3 00/ 0 0 0 00 0 00 0 o 0 o 00 00 ~0 00 0 0 0 0000 0 00 00 0 0*10 o *4e Dye 1 2 15 4 5 CH 3

CO

CO 2 Et CH 3 CO 2 Et

RH

H

CH

CO2H R02 C0 2

H

C0 2

H

CH

H

)\-max c-max (x 10 4 (methanol) 516 4.62 573 5.56 576 5.76 506 3.90 560 5.25 Table II Benzoylacetonitrile Merocyanine Dyes General Structure: 0 0~ .NI0R R a =CH-CH=o 7N 2, C 2 t t, a a.o i 04 to a Dye 6 7 8 9 n-C 6 H 1 3s O 2

NH

CH 3 so0 2

NH

CH 3 so 2

NH

H

R 2 X-max c-max (x 10 4 (methanol) CH 3 445 7.32 C 3

H

7 446 7.86 n-C 6 H 13 447 7.6 CH 3 449 -27- Table II-A Arylidene Dy General Structure: 0

,R

,:-Pr0 2 CCH -CH=.

CH'

Dye R -ma (methanol) H 424 3.

11 CH 3 423 3, 0 0 Table III 0. 0 0 0 15Benzoylacetonitrile Ar 0 0 General Structure: 1 ___CH 3 0 0 Q0R CN Dye R 1 R2 R 12 i-Pr0 2

CCH

2 i-Pr0 2

CCH

2

C

3

H

7 13 C 2

H

5 CF 3 CH 2 0 2

CCH

2 CH 3 14 i-Pr 2 CCH 2 i-Pr0 2

CGH

3 CH 3

C

2

H

5 CF 3 CH 2 O0 2

CCH

2

C

3 H 7 es

NHSO

2 Ph x (x l0 4 98 86 ylidene Dyes 3 =*-NI1S0 2

R

X-max c-max (x (methanol) 426 439 420 430 4.27 4.2 4.25 -28- Table IV Pyrazolone Nerocyanines Dyes General Structure:

R

3 o

R

4 aO\ .KN-C z \R3 1 2 R Dye R 1 R2 16 C 2

H

5 CH 3 R3 R4 )X-max emax (x 104) (methanol) 0 0 0 0 0 0 o a0 o0 0 00000 0000 CO 2

H

450 452 7.4 7. 19 i7 C 2 H 5 CH 3 C 2

H

18 1 a .=CH-CH=GH-CH=*. "R 3

CH

2 CH 3 \CH 3 )\-max 562 nm (methanol) c-max 11.9 x 10 4 Table V Barbituric Acid Merocyanines Dyes General Structure: 4 4 4 Dye R1 X.-max e-max (x 104) (methanol) 442 10.70 19 CH 2 PhCO 2 H C 2 H 5 C 2 H 5 L, wwdw 4 0"90 o 0 00 0 00 0 0 0 0 0 00 00 00 00 0 0 0 0000 0 00 00 0 0 00 0 0 -29- Table VI Benzoxazole Benzoylacetonitrile Merocyanine Dyes General Structure: 00=0 3 Dye 21 22 15 23 24 26 27 28 29 31 32 33 34 36 37 38 39 t/0 '1 0

CN

MeOEtSO 2

NH

Me0EtSO 2 NiH Me SO 2

NH

Me SO2N MeOEtSO 2Nil EtSO 2

NHI

EtS 2

NH

MeOEtSO 2

NH

HexS 2 N MeOEtSO 2NH Me SO 2

NH

CO2 EtOEtOEtSO 2

NH

EtOEtOEtSO 2

NH

PrS 2 N Me Et Et MeQEt CH 2 PhCO 2

H

MeQEt MeQEt Et Me MeQEt MeOEt MeOEt CH 2 PhCO 2

H

Me Me Me Et Et Et MeOEtSO 2

NH

MeS0 N MeOEtSO 2

NH

Hex SO 2N Me SO 2N Pr SO 2

NH

PrSO 2

NH

Pr SO 2

NH

MeSO 2N MeSO 2

NH

MeOEtSO 2

NH

MeS0 N HexSO 2

NH

MeS 2 N MeSO 2N MeS 2 N Pr SO 2

NH

MeS 2 N PrS 2 2

NH

MeS 2 N 0000 6 90 60 0 rS 2 1NH Me Me SO 2

NH

41 MeS0 2 NH Et EtS0 2

NH

42 EtS 2 'NH Et EtSO 2

NH

43 BuSO 2 NH Et MeSO 2

NH

44 BuS 2 NH Et CO 2

H

BuSO NH Me MeS0 2

INH-

46 MeS 2 NH Et BuS0 2

NH

Table VII Miscellaneous Dyes 0 0 15 0 0 0 C 00 "00/ 1-2 000 0 C9 0 -@3 )~mx=502 nm e-max =5.47 x 10 4 0000 48 CN 0~ 0 OH a 4 49 N==N CO 2

H

-31- 2 H

CH

0 -N=N-el

N

OH

r I SO CH3 1 51NH *-NO2 6SO 2 00 SO NH 2

N

C'0 2 2 000: CN 2 0000 '"NHSO.,C 2 3 CH 3

CN

53

CN

a NHS S 2 CH 3 -32- NH SO 2

CH

.~CH=f c 3 0 0 0 0 0 C 0 C 0 0o 0 00 0 ).X-max 500 nrni C-max 5.82 x 10 4 Table VIII Arylidene Dyes General Structure: (HOOC )x R 3 k 7 n 2

R

0000 0 1 04 0 00 00 1 Dye 56 57 58 59 61 62 63 1-Ph 1 2 3 4 Substn. x R R 3 R Position CH 3 H CH 3 1 4 C 2 H 5 H CH 3 1 4 n-C 4

H

9 H CH 3 1 4 CH 3 H CONC 2 H 5 1 4 i-C H 7 0C H 2

CH

3

CH

3 1 4 37 02 3 3 )X-max (nm) 466 471 475 508 430 457 475 477 e-max (10)4 3 .73 4.75 4.50 5 3 .34 3 .78 4.55 4.92 CH 3 C 2

H

5 n-C4H9 CH 3 CH 3 CH 3 3,5 3,5 3,5 64 66 67 68 69 71.

-33i-C H OCCH 2 i-C H 0CqH 2 i-c H OCCH-

H

CH 3

H

CH 3 CH 3 CH 3 0 COQEt COQEt CF 3 Ph 3,5 3,5 4 4 3,5 4 4 4 420 434 420 573 502 512 507 477 3 .62 3 3 .94 5.56 4.83 6 .22 4.58 4.54

CHB

3 CH 3 C 2 H 5

CHB

3 CH 3 a a

C

00 a a 0 00 00 a o '1 0 a 0 90 a

C

0000 0~~f 0 15 11 72 GB 3 H COBn 3 1 4 0 506 5.36 Table IX Oxazole and Oxazoline Pyrazolone Merocyanine Dyes 0 GB 3 0 _/co02 H 73 a N- -aZ, CP 3 oP 3 O 3O 2

H

G

3 74 0 CH 3 01 a =GH-CH=. N-o ,O~-C0 H c9 3 'N1 7 =~Nl 2 1 3 CEi 3 0 =CH-CH=. 0 NN P co H CNz C9 1 .1 1 -34- 0 /0 N- .NHS0-O \NZ\N 2 "Il0=*/ 02 a 0 00 0 0 00 a 00 00 00 0 0 0 0 Q 0 Q 0 00 0 a 00 0 000 ~0 0Q

CIL

0

C

6 2 CH 2 CH 3 0 0

I

S

79 0

~N.

IN/0 0

LS

440k 40 04 4 0 I~/0 0 I LN CH 2 CH 3 0000 0 0 0 0 0. 09 00 0 00409 C 2

H

82 15 83 0 CH3 I NHS 2

CH

3 C 3" C6 2 CH 2 CH 3

CH

3 cf~ S 3 N 0 2\ o C 2

H

-36- /I C 2H CO 2

H

00 0 0 0 0 0 0 0 co 00 0 0 0 0 0 0 00 0 0 0 00 00 400 0 H 3 1/

LJ

H C 0= 'N 0 H 3 C\ /0 1 1J 0=9/ H N 3 CH 3 0

NS

2 1 a

H

3 C C 3 'Ni 2' a 0000 6 0 0 60 0 -37- I~ INHSO 2 GCH 3 0 0 00 0 00 0 00 00.0 ~00.4 00 0 000 a 0 0 00 cfi 3

IY~~

91 0 CH 3 92 /0\ H0 2 C

T

GCl 3 93 ~S 0 0 0 /co 2l 0 I a SO 2CH 3

/LNI{S

02

O

0 2 2 0 k'/L0

H

=J-

zk"/LaC02H CH 3 cPI 3 Cil 3 ao2 -39- 0 CH I, S ns 2 1 l 3 Cg~ 3\ XCP 3 6 co2H Table X Oxazole and oxazoline Benzoylacetonitrile Nerocyanine Dyes 100 \0 .CH-CH= 015C0HO r" 0 0 Gl 0 C3

O

101 =CH-CH=C N 0= 200 3\ \N-NHSO CH 3 102~~ 3HNO, 252 aCH-CHC N11

CN

103 CH /0 0 c-K :-NHS 0 2 C H 20=0 31 CO 21H 010 0 a 9 10! 00010 1 a- /0= HO 2 f 0 Kc~ /CO CH CH 3 c a 0 N H HO 2 c co2 0 0 N1 0 UNHSO 2CH3

N

Nco 2 -41- 107 0 'N NHSO CH CH 3 CH 3 0

\XC

'N 2 H 108 0 00C 0 0 0 CID 0 0 I 0 7~/'N Cl

I

'N

I

S

0 "Lzz ONHSO CH CH CH

CN

0 2

H

109 CH 3 0 4 0644 444, 44 4 4.~ 0

CN

'N 2 H 0 110 =0\ >-NHSO 2 CH 3 0 6.9 0 0 00 0 0/ 0,/I 0 'c c' 0 2 H 4 0 CH' /0 -C=2

CH

3

N

-42- 112 0 0 UON___ NHSO CH 3 CH

'CN

3

CO

2 3 113 0 0

~CN

I

o 00 0 00 0 0 0 0. 00 a0 0 00 0 0.00 0 00 0 0044 0 00 0 '-n3-C9 3,11K

S

co2 114 115 116

CH

3 ci- I 3 C =0 0-.

CN

0 L -NHS 2 C H 2 CH 3 HO 2 c

IHGH

CH 3\ 0 0 0=0 >CO H

CN~

ul1 2

CH

2

CH

3 -43- 0 117 CH 0 2 c9 U GH 3H 118 CO0 H 0 0 oC 2

H

00 H 0 \N11 0 00 0 00 00 15 1 0 0 119 0 -CO H o i a CN

C

3 0 0 0U 000120 0 /,/*-C02H 0 i' a CN 2 C 2 5

N

Ch 3 4, -44- 0 0 /2~ 122 a'N N 11 3 0 123 0 -0 ,/I-O CN/0 CH 3 CH 2 so 2

NH

7 N a> 0 0 00 0 00.04 15 1/0=0" 0a124 *k 0 2 CH 3 CH 3 (CH 2 2 so 2

NH

C

Table XI Oxonol De

OH

41 HO -o 7N=CH-CH-CH_ N 00 0R wherein DYeQ R

R_

125 CH 3 CH 3 126 G 2

H

5 C 2 H The dye can be added directly to the hydrophilic colloid as a particulate solid or can be converted to a particulate solid after it is added to the hydrophilic colloid. One example of the latter technique is to dissolve a dye which is not water soluble in a solvent which is water soluble. When the dye solution is mixed with an aqueous hydrophilic colloid, followed by noodling and washing of the hydrophilic colloid (see Research Disclosure, Item 17643, cited above, Section II), the dye solvent is removed, leaving particulate dye dispersed within the hydrophilic colloid. Thus, any water insoluble dye which that is soluble in a water miscible organic solvent can be employed as a particulate dye in the practice of the invention, provided the dye is susceptible to bleaching under processing conditions-e.g., at alkaline pH levels. Specific examples o of contemplated water miscible organic solvents are o omethanol, ethyl acetate, cyclohexanone, methyl ethyl o oo o 15 ketone, 2-(2-butoxyethoxy)ethyl acetate, triethyl 0 1) 0 ophosphate, methylacetate, acetone, ethanol, and 09 dimethylformamide. Dyes preferred for use with these 0400 solvents are sulfonamide substituted arylidene dyes, specifically preferred examples of which are set forth about in Tables IIA and III.

In addition to being present in particulate form and satisfying the optical density requirements set forth above, the dyes employed in the under layer units must be substantially decolorized on processing. The term "substantially decolorized" is employed to mean that the dye in the under layer units raises the minimum density of the radiographic element when fully processed under the reference processing conditions, stated above, by no more than 0.1, preferably no more than 0.05, within the visible spectrum. As shown in the examples below the preferred particulate dyes produce no significant increase in the optical density of fully processed radiographic elements of the invention.

As indicated above, it is specifically contemplated to employ a UV absorber, preferably blended with the dye in each of crossover reducing I i i -46layers 111 and 113. Any conventional UV absorber can be employed for this purpose. Illustrative useful UV absorbers are those disclosed in Research Disclosure, Item 18431, cited above, Section V, or Research Disclosure, Item 17643, cited above, Section VIII(C).

Preferred UV absorbers are those which either exhibit minimal absorption in the visible portion of the spectrum or are decolorized on processing similarly as the crossover reducing dyes.

Overlying the under layer unit on each major surface of the support is at least one additional hydrophilic colloid layer, specifically at one halide emulsion layer unit comprised of a spectrally oOo sensitized silver bromide or bromoiodide tabular grain emulsion layer. At least 50 percent (preferably at least 70 percent and optimally at least 90 percent) of CI 000 °oo° a the total grain projected area of the tabular grain o00 ^ooS emulsion is accounted for by tabular grains having a thickness less than 0.3 pm (preferably less thxn 0.2 pm) and an average aspect ratio of greater thar.; 5:1 (preferably greater than 8:1 and optimally at least oo° 12:1). Preferred tabular grain silver bromide and I 5 bromoiodide emulsions are those disclosed by Wilgus et al U.S. Patent 4,434,226; Kofron et al U.S. Patent 4,439,530; Abbott et al U.S. Patents 4,425,425 and 4,425,426; Dickerson U.S. Patent 4,414,304; Maskasky U.S. Patent 4,425,501; and Dickerson U.S. Patent 4,520,098.

Both for purposes of achieving maximum imaging speed and minimizing crossover the tabular grain emulsions are substantially optimally spectrally sensitized. That is, sufficient spectral sensitizing dye is adsorbed to the emulsion grain surfaces to achieve at least 60 percent of the maximum speed attainable from the emulsions under the contemplated conditions of exposure. It is known that optimum spectral sensitization is achieved at about 25 to 100 -47percent or more of monolayer coverage of the total available surface area presented by the grains. The preferred dyes for spectral sensitization are polymethine dyes, such as cyanine, merocyanine, hemicyanine, hemioxonol, and merostyryl dyes.

Specific examples of spectral sensitizing dyes and their use to sensitize tabular grain emulsions are provided by Kofron et al U.S. Patent 4,439,520.

Although not a required feature of the invention, the tabular grain emulsions are rarely put to practical use without chemical sensitization. Any convenient chemical sensitization of the tabular grain 0° 0 emulsions can be undertaken. The tabular grain o emulsions are preferably substantially optimally (as o 15 defined above) chemically and spectrally sensitized.

o °Useful chemical sensitizations, including noble metal B gold) and chalcogen sulfur and/or o6 selenium) sensitizations as well as selected site epitaxial sensitizations, are disclosed by the patents cited above relating to tabular grain emulsions, particularly Kofron et al and Maskasky.

6oo, In addition to the grains and spectral sensitizing dye the emulsion layers can include as vehicles any one or combination of various 25 conventional hardenable hydrophilic colloids alone or in combination with vehicle extenders, such as latices and the like. The vehicles and vehicle extenders of o000oo o the emulsion layer units can be identical to those of the interlayer units. The vehicles and vehicle extenders can be selected from among those disclosed by Research Disclosure, Item 17643, cited above, Section IX. Specifically preferred hydrophilic colloids are gelatin and gelatin derivatives.

The coating coverages of the emulsion layers are chosen to provide on processing the desired maximum density levels. For radiography maximum density levels are generally in the range of from -48about 3 to 4, although specific applications can call for higher or lower density levels. Since the silver images produced on opposite sides of the support are superimposed during viewing, the optical density observed is the sum of the optical densities provided by each emulsion layer unit. Assuming equal silver coverages on opposite major surfaces of the support, each emulsion layer unit should contain a silver coverage from about 18 to 30 mg/dm 2 preferably 21 2 to 27 mg/dm It is conventional practice to protect the emulsion layers from damage by providing overcoat o layers. The overcoat layers can be formed of the same vehicles and vehicle extenders disclosed above in co 15 connection with the emulsion layers. The overcoat layers are most commonly gelatin or a gelatin S° derivative.

To avoid wet pressure sensitivity the total hydrophilic colloid coverage on each major surface of 2 the support must be at least 35 mg/dm 2 It is an observation of this invention that it is the total I hydrophilic colloid coverage on each surface of the support and not, as has been generally believed, simply the hydrophilic colloid coverage in each silver j 25 halide emulsion layer that controls its wet pressure sensitivity. Thus, with 10 mg/dm 2 of hydrophilic colloid being required in the interlayer unit for coating uniformity, the emulsion layer can contain as little as 20 mg/dm 2 of hydrophilic colloid.

To allow rapid access processing of the radiographic element the total hydrophilic coating coverage on each major surface of the support must be less than 65 mg/dm 2 preferably less than mg/dm 2 and the hydrophilic colloid layers must be substantially fully forehardened. By substantially fully forehardened it is meant that the processing solution permeable hydrophilic colloid layers are k -49forehardened in an amount sufficient to reduce swelling of these layers to less than 300 percent, percent swelling being determined by the following reference swell determination procedure: (a) incubating said radiographic element at 38 0 C for 3 days at 50 percent relative humidity, measuring layer thickness, immersing said radiographic element in distilled water at 21°C for 3 minutes, and determining the percent change in layer thickness as compared to the layer thickness measured in step This reference procedure for measuring forehardening is disclosed by Dickerson U.S. Patent 4,414,304. Employing this reference procedure, it is preferred that the hydrophilic colloid layers be 15 sufficiently forehardened that swelling is reduced to o o o less than 200 percent under the stated test conditions.

Any conventional transparent radiographic 0 0 element support can be employed. Transparent film supports, such as any of those disclosed in Research Disclosure, Item 17643, cited above, Section XIV, are 0g04 all contemplated. Due to their superior dimensional o a l rstability the transparent film supports preferred are polyester supports. Poly(ethylene terephthalate) is a specifically preferred polyester film support. The 25 support is typically tinted blue to aid in the examination of image patterns. Blue anthracene dyes are typically employed for this purpose. In addition to the film itself, the support is usually formed with a subbing layer on the major surface intended to receive the under layer units. For further details of support construction, including exemplary incorporated anthracene dyes and subbing layers, refer to Research Disclosure, Item 18431, cited above, Section XII.

In addition to the features of the radiographic elements of this invention set forth above, it is recognized that the radiographic elements can and in most practical applications will contain ~a~llPr- ~n~3lriRB; re~ -r 0 additional conventional features. Referring to Research Disclosure, Item 18431, cited above, the emulsion layer units can contain stabilizers, antifoggants, and antikinking agents of the type set forth in Section II, and the overcoat layers can contain any of variety of conventional addenda of the type set forth in Section IV. The outermost layers of the radiographic element can also contain matting agents of the type set out in Research Disclosure, Item 17643, cited above, Section XVI. Referring further to Research Disclosure, Item 17643, incorporation of the coating aids of Section XI, the 0*o plasticizers and lubricants of Section XII, and the Santistatic layers of Section XIII, are each 15 contemplated.

Examples The invention can be better appreciated by reference to the following specific examples: Screens The following intensifying screens were employed: Screen X This screen has a composition and structure corresponding to that of a commercial, general purpose 25 screen. It consists of a terbium activated gadolinium oxysulfide phosphor having a median particle size of 7 0 0pm coated on a white pigmented polyester support in Sa Permuthane polyurethane binder at a total phosphor coverage of 7.0 g/dm 2 at a phosphor to binder ratio of 15:1.

Screen Y This screen has a composition and structure corresponding to that of a commercial, medium resolution screen. It consists of a terbium activated gadolinium oxysulfide phosphor having a median particle size of 7 pm coated on a white pigmented polyester support in a Permuthane

TM

polyurethane -51binder at a total phosphor coverage of 5.9 g/dm 2 at a phosphor to binder ratio of 15:1 and containing 0.017535% by weight of a 100:1 weight ratio of a yellow dye and carbon.

Screen Z This screen has a composition and structure corresponding to that of a commercial, high resolution screen. It consists of a terbium activated gadolinium oxysulfide phosphor having a median particle size of pm coated on a blue tinted clear polyester support

TM

in a Permuthan M polyurethane binder at a total 2 phosphor coverage of 3.4 g/dm at a phosphor to binder ratio of 21:1 and containing 0.0015% carbon.

Radiographic Exposures Assemblies consisting of a double coated radiographic element sandwiched between a pair of intensifying screens were in each instance exposed as follows: The assemblies were exposed to 70 KVp X-radiation, varying either current (mA) or time,

TM

using a 3-phase Picker Nedical (Model VTX-650) X-ray unit containing filtration up to 3 mm of aluminum. Sensitometric gradations in exposure were achieved by using a 21-increment (0.1 log E) aluminum S 25 step wedge of varying thickness.

Element A (example) (Em.LC)LXOA(Em.HC) i Radiographic element A was a double coated I radiographic element exhibiting near zero crossover.

Radiographic element A was constructed of a low crossover support composite (LXO) consisting of a blue-tinted transparent polyester film support coated on each side with a crossover reducing layer consisting of gelatin (1.6g/m 2 containing 320 mg/m 2 of a 1:1 weight ratio mixture of Dyes 56 and 59.

Low contrast (LC) and high contrast (HC) emulsion layers were coated on opposite sides of the 1..

0O o o 0o 4 4 110 I I Lr Ili-- -52support over the crossover reducing layers. Both emulsions were green-sensitized high aspect ratio tabular grain silver bromide emulsions, where the term "high aspect ratio" is employed as defined by Abbott et al U.S. Patent 4,425,425 to require that at least percent of the total grain projected area be accounted for by tabular grains having a thickness of less than 0.3 pm and having an average aspect ratio of greater than 8:1. The low contrast emulsion was a 1:1 (silver ratio) blend of a first emulsion which exhibited an average grain diameter of 3.0 pm and an average grain thickness of 0.13 pm and a second emulsion which exhibited an average grain diameter of 1.2 pm and an average grain thickness of 0.13 pm.

The high contrast emulsion exhibited an average grain diameter of 1.7 pm and an average grain thickness of 0.13 pm. The high contrast emulsion exhibited less polydispersity than the low contrast emulsion. Both the high and low contrast emulsions were spectrally sensitized with 400 mg/Ag mol of 9-ethyl-3,3'-bis(3-sulfopropyl)oxacarbocyanine hydroxide, followed by 300 mg/Ag mol of potassium iodide. The emulsion layers were each coated with a silver coverage of 2.42 g/m 2 and a gelatin coverage 2 of 3.22 g/m 2 Protective gelatin layers (0.69 g/m 2 were coated over the emulsion layers. Each of the gelatin containing layers were hardened with bis(vinylsulfonylmethyl) ether at 1% of the total gelatin.

When coated as described above, but symmetrically, with Emulsion LC coated on both sides of the support and Emulsion HC omitted, using a Screen X pair, Emulsion LC exhibited a relative log speed of 98 and an average contrast of 1.8. Similarly, Emulsion HC when coated symmetrically with Emulsion LC omitted exhibited a relative log speed of 85 and an average contrast of 3.0. The emulsions thus differed Ffs~i- -i ii I oo o a o o o .4 oo o 0 4 4 o a o o0 0 0 -53in average contrast by 1.2 while differing in speed by 13 relative log speed units (or 0.13 log E).

When Element A was tested for crossover as described by Abbott et al U.S. Patent 4,425,425, it exhibited a crossover of 2%.

Element B (control) (Em. L)HXOB(Em. L) Radiographic element B was a conventional double coated radiographic element exhibiting extended exposure latitude.

Radiographic element B was constructed of a blue-tinted transparent polyester film support lacking the crossover reducing layers of radiographic element A. Identical emulsion layers were coated on opposite sides of the support. The emulsion employed 15 was a green-sensitized polydispersed silver bromoiodide emulsion. The same spectral sensitizing dye was employed as in Element A, but only 42 mg/Ag mole was required, since the emulsion was not a high aspect ratio tabular grain emulsion and therefore required much less dye for substantially optimum sensitization. Each emul'ion layer was coated to 2 provide a silver coverage of 2,62 g/m and a gelatin coverage of 2.85 g/m 2 Protective gelatin layers (0.70 g/m 2 were coated over the emulsion layers.

Each of the layers were hardened with bis(vinylsulfonylmethyl) ether at 0.5% of the total gelatin.

When coated as described above, using a Screen X pair, the film exhibited a relative log F speed of 80 and an average contrast of 1.6.

When Element B was tested for crossover as described by Abbott et al U.S. Patent 4,425,425, it exhibited a crossover of Element C (control) (Em.MC)HXOC(Em.MC) Radiographic element C was a conventional double coated radiographic element of a type employed on occasion for chest cavity examinations.

0 C 0 00 0 0 0 Oqo oo 0 0 04 as* 4 4 0 a o a a i oo a -54- Radiographic element C was constructed like radiographic element P, except that medium contrast emulsion layers (MC) were employed and the silver coverage of each emulsion layer was reduced to 1.93 2 g/m When coated as described above, using a Screen X pair, the film exhibited a relative log E speed of 80 and an average contrast of 2.6.

When Element C was tested for crossover as described by Abbott et al U.S. Patent 4,425,425, it exhibited a crossover of Element D (control) (Em.HC)HXOD(Em.HC) Radiographic element D was a conventional high aspect ratio tabular grain double coated 15 radiographic element of a type employed on occasion for chest examinations of subjects having low chest densities-i.e., children or adults of slight build.

Radiographic element D was constructed like radiographic element A, except that no crossover reducing layers were coated on the film support and a high contrast emulsion (HC) similar to that employed in radiographic element A was coated on both sides of the support.

When coated as described above, using a Screen X pair, the film exhibited a relative log E speed of 80 and an average contrast of 2.9.

When Element C was tested for crossover as described by Abbott et al U.S. Patent 4,425,425, it exhibited a crossover of Processing The films were processed in 90 seconds in a commercially available Kodak RP X-Omat (Model 6

B)T

rapid access processor as follows: development 20 seconds 1.t fixing 12 seconds at washing 8 seconds at 35°C, and drying 20 seconds at 65 0

C,

9f l"1 3 U

\CN

CH

3 3 where the remaining time is taken up in transport between processing steps. The development step employs the following developer: Hydroquinone 30 g l-Phenyl-3-pyrazolidone 1.5 g KOH 21 g NaHCO3 7.5 g

K

2 S0 3 44.2 g Na 2

S

2 0 5 12.6 g NaBr 35 g 0.06g Glutaraldehyde 4.9 g a Water to 1 liter at pH 10.0, and °a o the fixing step employs the following fixing So, 15 composition: 0 Ammonium thiosulfate, 60% 260.0 g 0 0 Sodium bisulfite 180.0 g 0 I 0 Boric acid 25.0 g Acetic acid 10.0 g Aluminum sulfate 8.0 g oo.. Water to 1 liter at pH 3.9 to I Sensitometry Optical densities are expressed in terms of diffuse density as measured by an X-rite MOdel 310

T

densitometer, which was calibrated to ANSI standard PH 2.19 and was traceable to a National Bureau of S. Standards calibration step tablet. The characteristic curve (density vs. log E) was plotted for each radiographic element processed. The average gradient, presented in Table XII below under the heading Contrast, was determined from the characteristic curve at densities of 0.25 and 2.0 above minimum density.

Assemblies Two assemblies were formed by placing Elei.ent A (satisfying the requirements of the invention) and each of the control elements, Elements B, C, and D, between a pair of intensifying screens as -56indicated in Table XII.

Table XII Contrast Screen/Film Assembly Average L_ung Hert I. Z(Em.LC)LXOA(EmHC)X 1.5 100 100 (Example) II. Z(Em. L)HXOB(Em. L)X 1.6 100 60 (Control) III.X(Em, L)HXOB(Em. L)Z 1.6 100 60 (Control) IV. X(Em. L)HXOB(Em. L)X 1.6 100 60 (Control) V. Z(Em.MC)HXOC(Em.MC)Z 2.6 115 20 (Control) VI. Z(Em.HC)HXOD(Em.HC)Z 2.9 130 20 (Control) VII. Z(Em.FLC)LXOE(Em.SHC)X 2.5 115 40 (Example) SVIII.Z(Em.SHC)LXOE(Em.FLC)X 1.5 69 266 (Example) O o 0 From Table XII it is apparent that assemblies 00 S°o I to IV all produced similar average contrasts when o0 0o 0 o 15 exposed between pairs of intensifying screens. The o°0 0 relative lung contrast, reported as 100, was selected oo as the contrast corresponding to a density of 1.8, which is a commonly accepted density for reading lung features in a radiograph. Relative heart contrast was then fixed as the contrast corresponding to a 1.0 log .oo, E lower exposure level, reflecting the fact that the heart normally absorbs about 10 times the X-radiation absorbed by the lungs and therefore allows only about one tenth of the X-radiation to reach the radiographic element in the heart image area that reaches the radiographic element in the lung image areas. While 0 'A Assembly I exhibited a lower contrast in its heart image areas than in its lung image areas, the heart image area for Assembly I was assigned a relative contrast of 100 for the purpose of comparing contrasts in the heart image areas of the various assemblies.

In comparing the relative heart area contrasts of Assemblies II to IV inclusive with that of Assembly I, it was observed that these latter assemblies provided only 60 percent of the contrast made available by Assembly I. The heart area contrasts were sufficiently low in the control assemblies as to

I

-57require skilled observation to distinguish significant imae features, whereas the much larger heart region relitive contrasts provided by Assembly I containing the double coated radiographic element of the inventioni were clearly discernible with much less visual effort. Assemblies II, III, and IV demonstrate that screen manipulation was ineffective in influencing the contrasts observed using the conventional extended latitude radiographic element.

Assemblies V and VI were included in Table XII to demonstrate the clear inferior image contrast observed in heart areas using conventional radiographic films of types sometimes used for chest a00 0 o 0 0 o o cavity examinations, but not specifically designed for 00 00 S 15 this use. With a relative contrast of only 20 in °°°heart areas, radiographic elements C and D clearly 0o o~o have limited utility in chest cavity examinations of heart areas.

It has been demonstrated in related investigations that double coated radiographic elements exhibiting crossover levels of less than percent and a first emulsion layer unit on one side of a transparent film support that is at least twice, preferably 2 to 10 times, and optimally 2 to 4 times, the speed of a second emulsion layer unit on the opposite side of the support exhibit different average contrasts when employed in combination with different screen pair combinations. From these related investigations it has been concluded tlht substitution of Film A for Film B in either of Assemblies III or IV would have produced higher average contrasts and, in all probability, higher contrasts in the heart image areas.

Assemblies V and VI were constructed to demonstrate that further advantages that can be realized by combining the teachings of Dickerson et al (III) with the teachings of this patent application.

-58- Element E (example) (Em.FLC)LXOE(Em.SHC) Radiographic element E was a double coated radiographic element exhibiting near zero crossover.

Radiographic element E was constructed of a low crossover support composite (LXO) identical to that of element A, described above.

Fast low contrast (FLC) and slow high contrast (SHC) emulsion layers were coated on opposite sides of the support over the crossover reducing layers. Both emulsions were green-sensitized high aspect ratio tabular grain silver bromide emulsions sensitized and coated similarly as the emulsion layers Soo o of element A.

When coated symmetrically, with Emulsion FLC "I 15 coated on both sides of the support and Emulsion SHC o°0\ omitted, using Screen X pair, Emulsion FLC exhibited +O00 a relative log speed of 113 and an average contrast of 1.98. Similarly, Emulsion SHC when coated symmetrically with Emulsion FLC omitted exhibited a relative log speed of 69 and an average contrast of 0o9oO 2.61. The emulsions thus differed in average contrast by 0.63 while differing in speed by 44 relative log speed units (or 0.44 log E).

When Element E was tested for crossover as described by Abbott et al U.S. Patent 4,425,425, it exhibited a crossover of 2%.

J Referring to Table XII, it is apparent that orienting the Film E with the fast low contrast emulsion layer adjacent the front screen Z produced results comparable to that obtained control Film C, except that a very advantageous doubling of relative contrast in the heart region was observed. When the Film E was reversed, contrast in the lung areas was reduced somewhat, but remained well within the range of obtaining useful information from lung image areas. At the same time relative contrast in the heart region was increased to 266. Thus, this I_ -59combination appears superior to all others in Table XII for obtaining image information from heart areas.

The foregoing comparisons provide a striking demonstration of the advantages which a radiologist can realize from the the present invention. The present invention offers the radiologist an improved diagnostic capability over an extended range of radiographic element exposures in studying a single radiographic image.

So 00 o 00 Sooo 0 00 002 0 o

OOQ

0000 ti 0 J

Claims

1. A radiographic element comprised of a transparent film support, first and second silver halide emulsion layer units coated on opposite sides of the film support, and means for reducing to less than 10 percent crossover of electromagnetic radiation of wavelengths longer than 300 nm capable of forming a latent image in the silver halide emulsion layer units, said crossover reducing means being decolorized in less than 90 seconds during processing of said emulsion layer units, characterized in that the first and second silver halide emulsion layer units each contain a spectral sensitizing dye, the crossover reducing means is comprised of a o oooo hydrophilic colloid layer interposed between at least one of said silver halide emulsion layer units and said support o 0 containing a particulate dye capable of absorbing o electromagnetic radiation to which said silver halide emulsion 0 layer unit on the opposite side of the support is responsive, o the first silver halide emulsion layer unit exhibits an average contrast of less than 2.0, based on density measurements at 0.25 and 2.0 above minimum density and the second silver halide emulsion layer unit exhibits an average contrast of at least 2.5, based on density measurements at 0.25 and 2.0 above minimum density, Slthe contrast of the first silver halide emulsion layer unit being determined with the first silver halide a emulsion unit replacing the second silver halide emulsion unit to provide an arrangement with the first silver halide emulsion unit present on both sides of the transparent support and the contrast of the second silver halide emulsion layer unit being determined with the second silver halide emulsion unit replacing the first silver halide emulsion unit to provide an arrangement with the second silver halide emulsion layer unit present on both sides of the transparent support.

2. A radiographic element according to claim 1 -61- further characterized in that the first silver halide emulsion layer unit exhibits an average contrast that differs by 0.5 to from that of the second silver halide emulsion layer unit.

3. A radiographic element according to claim 2 further characterized in that the first silver halide emulsion layer unit exhibits an average contrast that differs by 1.0 to from that of the second silver halide emulsion layer unit.

4. A radiographic element according to any one of claims 1 to 3 inclusive further characterized in that said crossover reducing means decreases crossover to less than percent. A radiographic element according to claim 4 further characterized in that said crossover reducing means decreases crossover to less than 3 percent.

6. A radiographic element according to any one of S claims 1 to 5 inclusive further characterized in that the a a o S first silver halide emulsion layer unit exhibits a speed that is at least equal to that of the second silver halide emulsion layer unit.

7. A radiographic element according to claim 6 further characterized in that the first silver halide emulsion layer unit exhibits a faster speed than that of the second silver halide emulsion layer unit.

8. A radiographic element according to any one of claims 1 to 7 inclusive further characterized in said silver halide emulsion layer units are comprised of emulsions in which tabular silver halide grains having a thickness of less than 0.3 pm exhibit an average aspect ratio of greater than 5:1 and account for greater than 50 percent of the total grain projected area.

9. A radiographic element according to claim 8 further characterized in that said silver halide emulsion layer units are spectrally sensitized. A radiographic element according to claim 9 further characterized in said silver halide emulsion layer units are comprised of emulsions in which tabular silver halide grains having a thickness of less than 0.2 pm exhibit an average aspect ratio of greater than 8:1 and account for 39,~ .greater than 70 percent of the total grain projected area. 1Z O i -62-

11. A radiographic element accordin to any one of claims 7 to 10 inclusive further characterized in that said emulsion layer units and crossover reducing means are each comprised of hardenable hydrophilic colloid layers, said crossover reducing means includes a hydrophilic colloid layer interposed between one of said emulsion layer units and said support containing a particulate dye capable of absorbing radiation to which said emulsion layer unit coated on the opposite side of the support is responsive and at least mg/dm 2 of said hardenable hydrophilic colloid, said emulsion layer units contain a combined silver coating coverge sufficient to produce a maximum density on processing the range of from 3 to 4, a i I -63- a total of from 35 to 65 mg/dm 2 of processing solution permeable hardenable hydrophilic colloid is coated on each of said opposed major surfaces of said support, and said processing solution permeable hydrophilic colloid layers are forehardened in an amount sufficient to reduce swelling of said layers to less than 300 percent, percent swelling being determined by incubating said radiographic element at 38 0 C for 3 days at 50 percent relative humidity, measuring layer thickness, immersing said radiographic element in distilled water at 21 0 C for 3 minutes, and determining the percent change in S°layer thickness as compared to the layer thickness measured in step whereby said radiographic element exhibits high covering power, reduced crossover without emulsion desensitization, reduced wet pressure sensitivity, and can be developed, fixed, washed, and emerge dry to the touch in a 90 second process cycle consisting of development 24 seconds at fixing 20 seconds at washing 10 seconds at 350C, and drying 20 seconds at 65 0 C, where the remaining time is transport between processing steps, the development step employs the following developer: Hydroquinone 30 g l-Phenyl-3-pyrazolidone 1.5 g KOH 21 g NaHC0 3 7.5 g K 2 S0 3

44.2 g Na 2 S 2 0 5 12,6 g NaBr 35 g 5-Methylbenzotriazole 0.06g Glutaraldehyde 4.9 g Water to 1 liter at pH 10.0, and i r- -64- the fixing step employs the following fixing composition: Ammonium thiosulfate, 60% 260.0 g Sodium bisulfite 180.0 g Boric acid 25.0 g Acetic acid 10.0 g Aluminum sulfate 8.0 g Water to 1 liter at pH 3.9 to 12. A radiographic element according to any one of claims 1 to 11 substantially as herein described with reference to any one of the Examples. DATED: 25 February 1992 PHILLIPS ORMONDE FITZPATRICK Attorneys for: o EASTMAN KODAK COMPANY* 9740S ozt) 0 *0 o a o r*