JPH02264944A - X-ray image forming method - Google Patents

Abstract

PURPOSE:To enhance sensitivity and to drastically decrease an exposure dose as well as to form X-ray images for medical purposes with high sharpness by confining the crossover light of a photographic sensitive material to <=12% and the development progressing state of silver halide emulsions to a parallel type development. CONSTITUTION:The method for developing the photographic sensitive material for medical purposes having at least one photosensitive silver halide emulsion layer respectively on both sides of a transparent base comprises preparing the emulsion layers and/or crossover cutting layers in such a manner that the crossover light of this photographic sensitive material is <=12% and developing the X-ray image forming film for medical purposes in such a manner that the development progressing state of the silver halide emulsions of the films is the so-called parallel type development. Since the sensitivity is greatly improved by the image forming method constituted in such a manner, the exposure dose is drastically decreased and the X-ray images for medical purposes having the extremely high sharpness to completely surpass the sharpness of a system for a one-side screen photosensitive material are formed.

Description

DETAILED DESCRIPTION OF THE INVENTION (Prior Art) In recent years, methods for observing the inside of the human body without physically incising the body have made rapid progress and continue to develop. These include methods such as CT, MRr, PET, and ultrasonic diagnostics, and computer image processing continues to develop these methods into systems with higher diagnostic capabilities. In these diagnoses, the primary image is observed on a CRT, and the most sensitive material is either directly photographed on a CRT, or the information captured as a digital signal inside a computer is printed using semiconductor laser exposure. secondary copy by method. For this purpose, so-called CRT photosensitive materials (sensor imager photosensitive materials) are rapidly becoming popular.

However, 80% to 90% of imaging for medical and diagnostic purposes still relies on so-called conventional systems that use X-ray/fluorescent screens and silver halide recording materials. This method is convenient for both patients and physicians, and is relatively inexpensive to implement and maintain. Although some systems will likely be replaced by other systems as it can provide fairly sufficient information for primary diagnosis, it is thought that it will continue to be the main medical diagnostic method in the future.

Breast cancer among women has been rapidly increasing in the United States in recent years, and signs of this are also seen in Japan. Conventional methods that use X-rays/fluorescent screens and sensitive materials as a method for early detection of breast cancer
Systems are extremely important. However, for early detection of breast cancer, it is necessary to identify calcified lesions of several hundred micrometers, and for this reason, conventional systems prioritize sharpness at the expense of system sensitivity, and use a considerably large amount of X-rays for diagnosis. I've been irradiating it for this purpose. It goes without saying that a large amount of X-ray irradiation is harmful to the human body, and for this reason, there continues to be a need for means to reduce the exposure dose.

In response to this demand, Easttsan Kodak Co., Ltd. applied dyes dispersed in fine solid form to the lower layer of the emulsion layer as a crossover cant layer. We have provided the market with a photosensitive material for manual diagnostics, "TMM-1," which has a sharpness close to that of the system, and has greatly improved sensitivity by having photosensitive emulsion layers on both sides of the support. Details of this new technology are disclosed in US Pat. No. 4,803,150. However, this technology has not solved the problem; doctors still demand higher-sharp images, and single-sided screens/sensitive material systems, which have a high exposure dose, are still used at a high rate. .

(Objective of the present invention) The present invention solves the above-mentioned current situation by providing a photosensitive emulsion layer on both sides of the support to significantly improve the sensitivity and thereby significantly reduce the exposure dose. Ultra-high sharpness medical X that completely surpasses sensitive material systems
It is an object of the present invention to provide a line image forming method, and particularly to provide an extremely useful diagnostic method for breast cancer screening.

(Means for Achieving the Present Invention) The above objects of the present invention were achieved by the following method. That is, in a method for developing a medical photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on each side of a transparent support, the emulsion is processed so that the cross-over light of the photographic light-sensitive material is 12% or less. layer and/or crossover cut layer, and the development progress state of the silver halide emulsion of the medical X-ray imaging film is in a so-called parallel fashion.
The purpose was achieved by developing the image.

In the present invention, so-called parallel type (parallel type)
llel fashion) development is C, E, K
ennethMees and T, Il, Jam
Written by es' TIIE THEORY 0FTtlE
PH0TOGRAPHIC PROCESS T old RD EDITION (published by Macmillan)
”, page 333, T, II.

Jalmes' paper "JournaI of Ph1
sical Chemistry Do Do, 42 (1940
)"It is described in.

In addition, Akira Sasai, “Chemistry of Photography” (published by Shashin Kogyo Publishing)
Page 221 of °° states that (1) the average size of the developed silver particles increases...that is, the particles that are being developed gradually become fully developed; and (2) the average size of the developed silver particles increases. Two types of development process concepts are shown when the number of particles increases, and the parallel type (parallel type) of the present invention
(lel fashion) Development means a development process in which the former (1) development process exists at a higher rate than the (2) process. In the present invention, all the grains in the emulsion layer start developing at the same time, and the increase in density due to the increase in development time is simply due to an increase in the size of the developed silver particles, and the number of developed silver remains the same. This is the most thought-provoking state, and the closer to this state as possible, the more significant the effects of the present invention will be.

Recently, in 1987 at ICPS (Kol n. Furthermore, at the 1987 Autumn Conference of the Photographic Society of Japan, Mie, Sansui, and Tani et al. gave a presentation on the influence of the properties of silver halide emulsions on development speed, and included the above-mentioned (1) and (2). ) development processes were defined as parallel development and granular development, respectively, and a discussion was developed.

In the present invention, the maximum density (Dmax) obtained when a sensitive material sufficiently exposed to light is developed using the system of the present invention and the density (Fog) obtained when processed without exposure are 1/34 degrees (-
(Dmax + Fo g) In particular, it is characterized by being 50 times or more and 200 times or less.

To confirm whether the parallel development of the present invention has been achieved, directly observe the particles in the process of development using an optical microscope in a system in which the emulsion is coated in a thin layer so that there is no bulk, or by performing low pH development in the middle of development. 2. Soak in stop solution or at liquid nitrogen temperature. T11 can be easily recognized by stopping the development by intense cooling, and then taking out the silver halide grains from the hydrophilic colloid layer and observing them with an electron microscope.

As a means for realizing the parallel type development of the present invention, first, it is possible to use a developer that easily causes parallel type development. As such a developer, commercially available developer for color paper CP20 (manufactured by Fuji Photo Film Co., Ltd.) is used.
and general black and white negative developer D76. The processing conditions for these developers are generally 3 minutes and 30 seconds at 33°C for CP2O and 4 or 7 minutes at 20°C for D76, but in the present invention, the pH of the developer is set to 10.5 to 10.5.
High image quality can be achieved by reducing the development processing time to 60 seconds or less while maintaining sensitivity by raising the processing temperature to around 12"C, raising the processing temperature to 30-40"C, or combining these methods. This is a useful method both for speeding up processing and for speeding up processing.

On the other hand, Xomat RP Developer (E
asttsanKodak), RD [[I and Hi
RENDOL (both manufactured by Fuji Photo Film Co., Ltd.) is mostly parallel type (Parallel fa).
However, even in such a developer, the parallel type ( Parallel f
ashion) development can be realized.

JP-A No. 63-73244 has an Agl content of 3°0 to 1.
Although a method for achieving some of the effects of the present invention using 5.1 mol% AgBr + tabular grains is described, this invention is insufficient in terms of crossover cut and cannot achieve the effects of the present invention. do not have.

For example, Research Disclosure No. 176, pages 28-30 (RD-17
Any of the known methods and known processing solutions for black-and-white photographic processing, such as those described in 643), can be applied. The processing temperature is normally selected between 18°C and 50"C, but temperatures below 18°C or above 50"C may also be used, although in the present invention an automatic processor at 30-45°C is used. Developing agents for which rapid processing is particularly preferred include dihydroxybenzene!I (e.g. hydroquinone), 3-pyrazolidones (e.g. 1-phenyl-3
- vilazolidone), aminophenol l! [(For example, N-methyl-P-aminophenol and the like can be used alone or in combination. The developer generally contains other known preservatives, alkaline agents, pH buffers, antifoggants, etc. If necessary, solubilizing agent, color toning agent, development accelerator (e.g. quaternary salt, hydrazine, benzyl alcohol), surfactant, antifoaming agent, water softener, hardener (e.g. glutaraldehyde), viscosity imparting agent. It may also contain agents.

As a special form of development processing, a developing agent is added to the light-sensitive material.
For example, hydrophobic developing agents that are contained in the emulsion layer and may be developed by processing the light-sensitive material in an alkaline aqueous solution are disclosed in Research Disclosure No. 16-9 (RD-16928). , U.S. Patent No. 2,7
39,890, British Patent No. 813,253 or West German Patent No. 17547.763. Such development treatment may be combined with silver salt stabilization treatment with thiocyanate.

As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as fixing agents can be used.

The fixing solution may contain a water-soluble aluminum salt as a hardening agent.

The photosensitive silver halide emulsion used in the present invention includes:
Silver chloride, silver chlorobromide, silver bromide, silver iodobromide, and silver chloroiodobromide can be used, but the following combinations with the aforementioned developer are preferred from the viewpoint of high sensitivity: Pyrazone - In the hydroquinone-based developer, silver iodobromide or silver chloroiodobromide is preferable, especially when the legal content is 411oI1
% to 20+*of% is preferred, while in metho-hydroquinone-based developers the iodine content is 6 moJ! % or less, preferably 3.0% or less, silver iodobromide, pure silver bromide, and silver chlorobromide are preferred, and among silver iodobromide, grains having a structure having a high iodine phase inside are particularly preferred.

Also, JP-A-60-230135 and JP-A No. 63-2565
The effect of the present invention becomes even more favorable when a compound that releases an inhibitor during development, as described in No. 3, is used in combination.

It is a well-known fact in the art that crossover light significantly reduces sharpness.

As a means for ensuring that the cross-over light of photographic light-sensitive materials is 12% or less, US Patent No. 4°130.42
9, JP-A-61-116354, etc. discloses a method of absorbing light with a wavelength matching the emission wavelength of an X-ray fluorescent screen using a sensitizing dye or dye.

Further, US Pat. No. 4,803,150 discloses a technique in which a dye is present in the form of a microcrystalline dispersion between a support and an emulsion layer so that the cross-over i-light is less than 10%. In addition, Japanese Patent Application No. 62-141111 describes a technique for fixing anionic dyes in a specific layer using cationic polymer latex, and Japanese Patent Application No. 62-3245
No. 75 discloses a technique in which the dye fixed layer is used as an undercoat layer on the support.0 The sensitive material of the present invention can use any of these methods, but the dye-colored layer is an undercoat layer. Preferably, the dye is disclosed in Japanese Patent Application No. 62-32457.
5. In particular, the dye must be fixed by the method described in US 4.
It is preferable that it is fixed to the undercoat layer in the form of a microcrystalline dispersion as described in , 803, 150.

In the present invention, these methods can be combined as appropriate.

The dispersion layer of the dye in the form of microcrystalline particles preferably used in the present invention includes general formulas (1), (II), (I[[),
A filter dye layer of a microcrystalline dispersion of a compound of (IV) or (V) is used.

- Pattern hole N) R1 S General formula (n) R1 cs General formula (I [I) A = L + + L z -L s ÷1-A'
General formula (IV) A+L+ L! →T1B General formula (V) In the formula, A SA ' represents a substituted or unsubstituted acidic nucleus having a carboxyphenyl group, sulfamoyl group, or sulfonamidophenyl group, and examples of the acidic nucleus include 2-viraprin-5-one, rhodanine, selected from hydantoin, thiohydantoin, 2,4-oxazolidinedione, isoxacillinone, barbital acid, thiobarbic acid, indandione, pyrazolopyridine, and hydroxypyridone. B represents a substituted or unsubstituted basic nucleus having a carboxyl group, sulfamoyl group, or sulfonamide group; the basic nucleus is selected from the group consisting of pyridine, quinoline, indolenine, oxazole, penduoxazole, naphthoxazole, and pyrrole; To be elected. R
is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, R+ and Rz are each a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or an acyl group, and R3 and Rt are carbon atoms forming a 5- to 6-membered ring. Rs and Rh each represent a hydrogen atom, a hydroxy group, a carboxy group, an alkyl group, an alkoxy group, or a halogen atom, and R4 and R1 each represent a hydrogen atom, or R1 and R4 or R8 and R3 each represent a Hail the metal atoms necessary to form a 6-membered ring, Ll,
Lt, L each represent a substituted or unsubstituted methine group, x and y each represent an electron-withdrawing group, and either X or Y has at least one carboxyphenyl group or a sulfamoylphenyl group, 1m having a sulfonamidophenyl group represents 0 or 1, n represents 011 or 2, and P represents 0 or 1.

Next, specific examples of dyes used in the present invention will be given, but the present invention is not limited thereto.

[-7 ■-11 ■-12! ■-13 H3 ■-14 ■-15 ■-16 ■-17 ShitI3 m-3 ■ ■-5 ■-6 ■-8 +11-9 ■-1 ctt's ■ C,lIs V-9 Ct 11 s zHs ■-12 V-5 Cen H5 H3 V-8 ■-13 ■-15 Cz It s ■-16 V-4 ■-1 C2H4 Js CHl CHl The dye used in the present invention is disclosed in the International Patent Application Publication (WO) 8
B104794, European Patent (BP) 02747
No. 23A1, JP-A-52-92716, JP-A No. 55-15
No. 5350, No. 55-1, No. 55351, No. 61-205934, No. 4B-68623, U.S. Patent No. 2527583, No. 3486897, No. 374
It can be easily synthesized by the methods described in No. 6539, No. 3933798, No. 4130429, No. 4040841, and the like.

Although the dyes useful in this invention can be used in any useful amount to absorb light, it is particularly advantageous to use them in amounts and locations such that they are solubilized and washed out during the development process. be. If it is desired to absorb only a small amount of light, only a small amount of dye is needed. If greater amounts of light absorption are desired, larger amounts of dye can be used as long as the coloration level remains acceptable for the particular photographic element. The dye is preferably present in the photographic element in an amount of 10 to 1000 cm/po per side.

The dyes useful in this invention are in the form of solid particulate microcrystalline dispersions for inclusion in layers, such as hydrophilic colloid layers, coated on photographic elements. Microcrystalline dispersions can be formed by precipitating the dye in the form of a dispersion and/or by known milling methods, such as ball milling, sand milling or colloid milling, in the presence of a dispersant. The dye particles in the dispersion have an average diameter of less than 10 μm, more preferably less than 1 μm, particularly preferably less than 0.3 μm.

The mordant layer of the present invention contains an anionic dye with good decolorizing properties and a cationic polymer as a mordant as main materials, and a combination of a cationic polymer and a general anionic dye as shown below (Vl) is preferably used. In order to stably apply the combination of dye and mordant, some ingenuity is required. When the mordant layer is used as a layer between the support and the photosensitive emulsion layer and is coated simultaneously with the photosensitive emulsion layer, good coating properties can be obtained by providing an intermediate layer containing as little unnecessary anions as possible between the mordant layer and the photosensitive emulsion layer. It will be done. Also, adding the binder to the undercoat layer of the support,
In order to maintain a stable and good undercoat surface condition, it is recommended to use a nonionic surfactant in combination.

- Monka (Vl) R9 -(-A h -+ CHz -c Juice → B
)tL Xo Rt Q Rs In the formula, A represents an ethylenically unsaturated heptamer unit, R1
is a hydrogen atom or a lower alkyl group having 1 to about 6 carbon atoms,
L represents a divalent group having 1 to about 12 carbon atoms -
Rt, Rs and R4 are each the same or different 1
an alkyl group having ~20 carbon atoms, or 7
represents an aralkyl group or a hydrogen atom having ~20 carbon atoms, Rg, Rs and R4 may be interconnected to form a cyclic structure with Q, preferably R1
, Rj and R, only one is a hydrogen atom. Q is N or P, and Xo represents an anion other than iodide ion.

Examples of the ethylenically unsaturated heptamers of A include olefins (e.g., ethylene, propylene, 1-
butene, vinyl chloride, vinylidene chloride, isobutyne, vinyl bromide, etc.), dienes (e.g. butadiene, isoprene, chlorobrene, etc.), ethylenically unsaturated esters of fatty acids or aromatic carboxylic acids (e.g. vinyl acetate, allyl acetate, vinyl pionate, vinyl butyrate, vinyl benzoate), esters of ethylenically unsaturated acids (e.g. methyl methacrylate, butyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, octyl methacrylate, amyl acrylate, - ethylhexyl acrylate, benzyl acrylate, dibutyl maleate, diethyl fumarate, ethyl crotonate, dibutyl methylenemalonate, etc.), styrenes (e.g., styrene, α-methylstyrene, vinyltoluene, chloromethylstyrene, Chlorstyrene, dichlorostyrene, bromstyrene, etc.), unsaturated nitriles (e.g. acrylonitrile, methacrylaterile, allyl cyanide, crotonitrile, etc.). Among these, styrenes, 6A, which is particularly preferably a methacrylic acid ester, may contain two or more of the above monomers.

R1 is preferably a hydrogen atom or a methyl group from the viewpoint of polymerization reactivity.

From the viewpoint of alkali resistance, -C-N-R, - in the above formula, Rs is alkylene (for example, methylene, ethylene, trimethylene, tetramethylene), annealed,
represents an aralkylene (e.g. alkylene having an atom), R6 represents a hydrogen atom or R1, n is 1 or 2
is an integer.

Q is preferably N in view of the toxicity of the raw material.

X (El is an anion other than iodide ion, such as halogen ion (e.g. chloride ion, bromide ion, etc.)
, alkyl sulfate ions (e.g. methyl sulfate ion, ethyl sulfate ion, etc.), alkyl or aryl sulfonate ions (e.g. methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, etc.), nitrate ion, acetate ion, Contains sulfate ions. Among these, chloride ions, alkyl sulfate ions, arylsulfonate ions, and sulfate ions are particularly preferred.

The alkyl groups and aralkyl groups of R, R, and R1 include substituted alkyl groups and substituted aralkyl groups.

Examples of alkyl groups include unsubstituted alkyl groups, such as methyl, ethyl, propyl, isopropyl, t-butyl, hexyl, cyclohexyl, 2-ethylhexyl, and dodecyl groups; substituted alkyl groups, such as alkoxyalkyl groups; (e.g., methoxymethyl group, methoxybutyl group, ethoxyethyl group, butoxyethyl group, vinyloxyethyl group, etc.), cyanoalkyl group (e.g., 2-cyanoethyl group, 3-cyanopropyl group, etc.)
, halogenated alkyl group (e.g., 2-fluoroethyl group, 2-chloroethyl group, perfluoropropyl group, etc.)
, an alkoxycarbonylalkyl group (for example, an ethoxycarbonylmethyl group), an allyl group, a 2-butenyl group, a propakyl group, and the like.

Aralkyl groups include =, WIA aralkyl method, for example, benzyl group, phenethyl group, diphenylmethyl group, naphthylmethyl group, etc.; dimethylbenzyl group, 4-isopropylhensyl group, 4-octylbenzyl group, etc.), alkoxyaralkyl group (e.g., 4-methoxybenzyl group,
4-pentafluoropropenyloxybenzyl group, 4-ethoxybenzyl group, etc.), cyanoaralkyl group (e.g. 4-cyanohensyl group, 4-(4-cyanophenyl)
benzyl group, etc.), halogenated aralkyl group (e.g., 4-chlorobenzyl group, 3-chlorobenzyl group, 4-chlorobenzyl group,
bromobenzyl group, 4-(4-chlorophenyl)benzyl group, etc.).

The alkyl group preferably has 1 to 12 carbon atoms, and the aralkyl group preferably has 7 to 14 carbon atoms.

X is O to 90 mol%, preferably 0 to 50 mol%, and y is 10 to 99.9 mol%, preferably 10 to 95 mol%.

2 is 0.1 to 50 mol%, preferably 1 to 30 mol%.

B is a structural unit obtained by copolymerizing a copolymerizable monomer having at least two ethylenically unsaturated groups. Examples of B include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, tetramethylene glycol dimethacrylate, pentaerythritol tetramethacrylate, trimethylolpropane trimethacrylate,
Ethylene glycol diacrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate, tetramethylene glycol diacrylate, trimethylolpropane triacrylate, allyl methacrylate, allyl acrylate, diallyl phthalate,
Methylenebisacrylic acid, methylenebismethacrylamide, trivinylcyclohexane, divinylhenzene, N.

N-bis(vinylbenzyl)-N,N-dimethylammonium chloride, N,N-diethyl-N-(methacryloyloxyethyl)-N-(vinylhensyl(ammonium chloride, N,N,N'N1-tetraethyl-N
N'-bis(vinylhensyl(p-xylylenediammonium dichloride 1', NN'-bis(vinylbenzyl)-triethylenediammonium dichloride, N, N,
Examples include N'N'-tetrabutyl-N,N'-bis(vinylbenzyl)-ethylenediammonium dichloride. Among these, divinylhenzene and trivinylcyclohexane are particularly preferred from the viewpoint of hydrophobicity, alkali resistance, and the like.

Compound example Vl-1) x:y:z=47.5:47
．． 5: 5■-4) C11□ (CIICIIt now- x:y:z-45:45:10 ■-6) 11, C.

tHs y:z=80:20 y:z=95:5
It is 50 mg/po.

Next, preferred dyes that can be used in combination with cationic mordants in the present invention will be described.

Such dyes include, for example, British Patent No. 506385;
1,177.429, 1,311.884, 1,338,799, 1゜385.371, 1
, 467.214, 1.433, 102, 1.
No. 553,516, JP-A-48-85,130, No. 4
9-114゜420, 52-117.123, 55-161.233, 59-111,640,
Japanese Patent Publication No. 39-22,069, No. 43-13,168, U.S. Patent No. 3.247,127, No. 3.469.9
oxonol dyes having a pyrazolone nucleus or barbylic acid nucleus described in No. 85, No. 4.078,933, etc.;
U.S. Patent No. 2,533°472, U.S. Patent No. 3,379,53
No. 3, British Patent No. 1.278. ．． Other oxonol dye f4 described in No. 621 etc., British Patent No. 575.69
No. 1, No. 680.631, No. 599.623, No. 7
86.907, 907.125, 1. O45,
No. 609, U.S. Patent No. 4,255,326, JP-A-5
Azo dyes described in JP-A No. 9-211.043, etc., JP-A-50-100,116, JP-A No. 54-118,247,
Azomethine dyes described in British Patent No. 2,014,598, British Patent No. 750,031, etc., U.S. Patent No. 2,865
, 752, U.S. Patent No. 2.538.009, U.S. Pat. No. 2,688,541, U.S. Pat.
1,210.252, JP 50-40.625, JP 51-3,623, JP 51-10.927, JP 54-118,247, JP 48-3,286 ,
Azomethine dyes described in Japanese Patent Publication No. 59-37,303, styryl dyes described in Japanese Patent Publications No. 28-3,082, No. 44-16,594, No. 59-28,898, etc., British Patent No. No. 446,583, 1,335.4■-
Triarylmethane dye described in No. 6 22, JP-A No. 59-228,250, etc., British patent tube 1°075.65
No. 3, No. 1,153,341, No. 1,284,730
No. 1,475,228, No. 1,542,807, etc., U.S. Patent No. 2,84
Examples include cyanine dyes described in No. 3,486 and No. 3,294,539.

Representative dyes are shown below, but the present invention is not limited thereto.

■-3 ■-4 ■-5 ■-2 SO, to to 503 ■-9 OJa ■-1 ■-13 ■-14 (C14SO, (HzJ4sU3Na Next, the emulsion grains used in the present invention will be explained.

The sphere-equivalent average particle size of the same volume as the particles is preferably 0.4 μm or more. In particular, the narrower the particle size distribution, which is preferably 0.5 to 2.0 pm, the better.

The silver halide grains in the emulsion may have a regular crystal shape such as a cube or an octahedron, or may have an irregular crystal shape such as a spherical shape, a plate shape, a potato shape, etc.
It may have an irregular crystal form or a composite form of these crystal forms, it may consist of a mixture of particles of various crystal forms, and it may have a tabular shape with a particle diameter of 5 times or more the particle thickness. Particles are preferably used for the present invention (in particular, RESERRCHDISCL
O3URE Volume 225 Item 22534 P, 2
0-P, 58. January issue, 1983, and Japanese Patent Application Publication No. 1983
-127921 and 5B-113926).

The tabular silver halide grains can be produced by appropriately combining methods known in the art.

The tabular silver halide emulsion is manufactured by Cugnac.
and Chateau) ``Evolution of the Morphology of Silver Bromide Crystals During Physical Ripening'' Science. Industrial Photography, Volume 33, N11 (1962), pp, 121-
125, Duffin [Photographic Emulsion Chemistry'-(Photogr.
aphic emulsion Chea+1try
) J Focal Press
), New York, 1966, p-66-p, 72
, A, P, H.

Trivell+, W, F. Smith Photographic Journal (
Photographic Journal), 80
Volume, page 285 (1940), etc., but JP-A-58-127,921 and JP-A-58-113,927.
, JP 58-113.928, U.S. Patent No. 44395
It can be easily prepared by referring to the method described in No. 20.

In order to effectively utilize the effects of the present invention, it is necessary to apply a
(2) It is preferable that the above silver halide adsorbing substance be present. This silver halide adsorptive substance is used during grain formation.
Chemical sensitizers (e.g., gold or sulfur sensitizers) may be added at any time, such as immediately after grain formation, before or after ripening begins, or during ripening.
It is preferable to add the sensitizer before the chemical sensitizer is added or at the same time as the chemical sensitizer, and it must be present at least during the process of chemical sensitization.

As a condition for adding the silver halide adsorbent substance, the temperature is 30°C.
PH
, PAg may be optional, but at the time of chemical sensitization, the pH is 6 to 10. It is preferable that pAg is 7-9.

In the present invention, the silver halide adsorbing substances are aggravating dyes,
Or it means a type of photographic performance stabilizer.

Namely, azoles (e.g. benzothiazolium salts, penzimidazome salts, imidazoles, benzimidazoles, nitroindazoles, triazoles, benzotriazoles, tetrazoles, triazines, etc.); mercapto compounds [(e.g. mercaptothiazole) mercaptobenzothiazoles, mercaptoimidazoles, mercaptobenzimidazoles, mercaptobenzoxazoles, mercaptothiadiazoles, mercaptooxadiazoles, mercaptotetrazoles, mercaptotriazoles, mercaptopyrimidines, mercaptotriazines, etc.1; e.g. Thioketo compounds such as oxadorinthione; azaindenes (e.g. triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a,7) tetraazaindenes), pentaazaindenes, etc.); A number of compounds known as antifoggants or stabilizers can be mentioned as silver halide adsorbents.

Furthermore, purines or nucleic acids, or
36213, JP-A No. 59-90844, and the like are also usable adsorbent substances.

Among them, azaindenes, purines, and nucleic acids are particularly preferred and can be used in the present invention. The amount of these compounds added is 300 to 3000 cm per mole of silver halide.
, preferably 500 to 2500 mg.

As the silver halide adsorbing substance of the present invention, the sensitizing dye is
A desirable effect can be achieved.

As the sensitizing dye, cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopholarianine dyes, styryl dyes, hemicyanine dyes, oxonol dyes, hemioxonol dyes, etc. can be used.

Useful enhancing dyes for use in the present invention include, for example, U.S. Pat.
, No. 522,052, No. 3,619,197, No. 3,
No. 713,828, No. 3,615゜643, No. 3,6
No. 15,632, No. 3.617.293, No. 3,62
No. 8,964, No. 3703.377, No. 3,666
．． No. 480, No. 3.667.960, No. 3,679,
No. 428, No. 3,672,897, No. 3,769.0
No. 26, No. 3,556.800, No. 3,615,61
No. 3, No. 3,615,638, No. 3,615゜635
No. 3,705.809, No. 3,632.349, No. 3,677.765, No. 3770.449,
No. 3,770,440, No. 3,769,025, No. 3,745,014, No. 3,713,828, No. 3
, No. 567.458, No. 3,625,698, No. 2,
No. 526,632, No. 2,503.776, JP-A-4
8=76525, Belgian Patent No. 691,807, etc. The amount of sensitizing dye added is halogenated 1
It is preferably 300 to less than 20,001 g, preferably 500 to less than 1,000 g per 11 moles.

Specific examples of sensitizing dyes useful in the present invention are shown below.

C, Hs to SO+ 5O1- 3O,K O3K Among the above, cyanine dyes are particularly preferred.

A preferred embodiment is to use the sensitizing dye and the above-mentioned stabilizer together.

The sensitizing dye used in the present invention may be added after chemical sensitization and before coating.

The projected area diameter of the tabular emulsion of the present invention is 0.3 to 2.0a.
m, preferably 0.5 to 1.2 pm, and the distance between parallel planes (particle thickness) is 0.05 μm
~0.3 μm, especially 0.3 μm. The silver halide emulsion of the present invention preferably has an aspect ratio of 1 to 0.25 μm, and the aspect ratio is preferably 3 or more and less than 20, particularly 4 or more and less than 8. Silver halide grains account for more than 50% (projected area) of all grains, especially 70%
Among the tabular silver halide grains, which preferably have an average aspect ratio of 3 or more, particularly 4 to B, monodisperse hexagonal tabular grains are particularly useful grains.

The structure and manufacturing method of the monodisperse hexagonal tabular grains referred to in the present invention are as described in Japanese Patent Application No. 61-299155.

Methods for chemically sensitizing the silver halide emulsion used in the present invention include sulfur sensitization, selenium sensitization, reduction sensitization, gold sensitization, etc. in the presence of the silver halide adsorbing substance described above. Known methods can be used, used alone or in combination.

Among the noble metal sensitization methods, the gold sensitization method is a typical method and uses a gold compound, mainly a total complex salt. It may contain complex salts of noble metals other than pure metals, such as platinum, palladium, iridium, etc., a specific example of which is disclosed in U.S. Patent No. 2,448.06.
No. 0, British Patent No. 618.061, etc.

As the sulfur sensitizer, in addition to the sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines, etc. can be used. Specific examples are U.S. Patent Nos. 1,574,944 and 2.
, No. 278.947, No. 2,410,689, No. 2,
No. 728,668, No. 3,501,313, No. 3.6
56.955.

The combined use of sulfur sensitization using thiosulfate and gold sensitization can effectively exhibit the effects of the present invention.

As the reduction sensitizer, stannous salts, amines, formamidine sulfinic acid, silane compounds, etc. can be used.

The photographic emulsion used in the present invention contains silver halide in the chemical sensitization process of the present invention for the purpose of preventing capri during the manufacturing process, storage, or photographic processing of light-sensitive materials, or stabilizing photographic performance. Various compounds can be included in addition to the adsorptive substance. That is, azoles (e.g. benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles,
Bromobenzimidazoles, nitroindazoles,
benzotriazoles, aminotriazoles, etc.)
; Mercapto compounds (e.g. mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles 1, mercaptotetrazoles, mercaptopyrimidines, mercaptotriazines, etc.) ; Thioketo compounds such as oxadorinthione; azaindene (e.g. triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a,7) tetraazaindenes), pentaazaindenes, etc.); benzenethiosulfonic acid, benzenesulfinic acid, benzene Many compounds known as antifoggants or stabilizers can be added, such as sulfonic acid amides and the like.

In particular, nitrone and its derivatives described in JP-A-60-76743 and JP-A-60-87322, JP-A-60-8
Mercapto compound described in Publication No. 0839, JP-A-57
The heterocyclic compound described in JP-A-164735 and a complex salt of a heterocyclic compound and silver (for example, 1-phenyl-5-mercaptotetrazole 11) can be preferably used.

Even when a sensitizing dye is used as a silver halide adsorbing substance in the chemical sensitization step, spectral sensitizing dyes in other wavelength ranges may be added as necessary.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared using the present invention may contain coating aids, antistatic properties, smoothness improvement, emulsification dispersion, direct prevention, and improvement of photographic properties (e.g.
Various surfactants may be included for various purposes such as development acceleration, hardening agent, sensitization, etc.

For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene oxide adducts of silicones), alkyl esters of sugars. Nonionic surfactants such as; alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylenes Anionic surfactants such as alkylphenyl ethers; Ampholytic surfactants such as alkylbetaines and alkylsulfobetaines; Cationic surfactants such as aliphatic or aromatic quaternary ammonium salts, pyridinium salts, imidazolium salts can be used.

Among these, saponin, dodecylbenzenesulfonic acid Na salt, di-2-ethylhexyl α-sulfosuccinic acid N, a salt, p-octylphenoxyethoxyechnesulfonic acid N
anions such as a salt, dodecyl sulfur @ Na salt, triisopropylnaphthalene sulfonic acid Na salt, N-methyl-oleoyl taurine Na salt, dodecyltrimethylammonium chloride, N-oleoyl-N', N', N'- 1
- Cations such as limethylammoniodiaminoprobane bromide and dodecylpyridium chloride, betaines such as N-dodecyl-N, N-dimethylcarboxybetaine, N-oleyl-N, and N-dimethylsulfobutylbetaine, poly(average degree of polymerization) n-10) oxyethylene cetyl ether, poly(n=25) oxyethylene p-nonylphenol ether, bis[1-poly(n-15)
Nonions such as oxyethylene-oxy-2,4-(pentylphenyl)ethane can be particularly preferably used.

As antistatic agents, perfluorooctanesulfonyl salt, N-propyl-N-perfluorooctanesulfonylglycine Na salt, N-propyl-N-perfluorooctanesulfonylaminoethyloxypoly(n-3)oxyethylenebutanesulfonic acid Na salt, N-perfluorooctanesulfonyl-N', N', N'-1-limethylammoniodiaminopropane chloride, N-perfluorodecanoylaminopropyl-N', N'-dimethyl-N'- Fluorine-containing surfactants such as carboxybetaine, JP-A-60-80848, JP-A-61-112144
Nonionic surfactants, alkali metal nitrates, conductive tin oxide, zinc oxide, vanadium pentoxide, or composites of these doped with antimony, etc. Oxides can be preferably used.

In the present invention, U.S. Patent No. 299210 is used as a matting agent.
No. 1, No. 2701245, No. 4142894, No. 4
Homopolymers of polymethyl methacrylate or copolymers of methyl methacrylate and methacrylic acid as described in No. 396,706, organic compounds such as starch, silica,
Fine particles of inorganic compounds such as titanium dioxide, sulfuric acid, strontium barium, etc. can be used.

The particle size is 1.0 to 10 μm, especially 2 to 5 μm.
It is preferable that

In the surface layer of the photographic material of the present invention, in addition to the silicone compounds described in U.S. Pat.
Higher fatty acid esters, starch derivatives, etc. can be used.

Polyols such as trimethylolpropane, bentanediol, butanediol, ethylene glycol, and glycerin can be used as plasticizers in the hydrophilic colloid layer of the photographic material of the present invention.

As the binder or protective colloid that can be used in the emulsion layer, intermediate layer, and surface protective layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used. .

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfate esters; WI derivatives such as sodium alginate, dextran, and starch derivatives; Various synthetic hydrophilic polymeric substances such as single or copolymers of polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Can be used.

As the gelatin, in addition to lime-treated gelatin, acid-treated gelatin or enzyme-treated gelatin may be used (also, gelatin hydrolysates or enzymatically decomposed products can also be used).

Among these, it is preferable to use dextran or polyacrylamide with an average molecular weight of 50,000 or less together with gelatin.
The method described in No. 8405 is also effective in the present invention.

The photographic emulsions and non-photosensitive hydrophilic colloids of the present invention may contain inorganic or organic hardeners.

For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glitaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.)
, dioxane derivatives (2゜3-dihydroxydioxane, etc.), active vinyl compounds (1,3,5-)lyacryloyl-hexahytrose-) riazine, bis(vinylsulfonyl)methyl ether, N,N'-methylenebis[
β-(vinylsulfonyl)propionamide], etc.),
Active halogen compounds (2,4-dichloro-6-hydroxy-5-t-riazine, etc.), mucohalogen acid IW (mucochloric acid, mucophenoxychloroic acid, etc.) isoxazoles, dialdehyde starch, 2-chloro-6- Hydroxytriazinylated gelatin and the like can be used alone or in combination. Among them, JP-A-53-41
2211 53-57257, 59-162546,
The active vinyl compounds described in US Pat. No. 60-80846 and the active halides described in US Pat. No. 3,325,287 are preferred.

Polymer hardeners can also be effectively used as hardeners in the present invention.

Examples of the polymeric hardening agent used in the present invention include dialdehyde starch, polyacrolein, and U.S. Patent No. 3.396.0.
Polymers having aldehyde groups such as acrolein copolymers described in US Pat. No. 3,623.878, polymers having epoxy groups as described in US Pat.
No. 62,827, Research Disclosure Magazine 17
333 (1978), polymers having active ester groups as described in JP-A-56-66841, JP-A-56-142524, U.S. Patent No. 4.161. ,40
No. 7, JP-A-54-65033, Research Disclosure Magazine 16725 (1978), etc., polymers having an active vinyl group or a group that is a precursor thereof, etc. Preferred are polymers having a group that serves as an active vinyl group, or a group that serves as a precursor thereof, bonded to the polymer main chain by a long spacer as described in JP-A-56-142524. Polymers are particularly preferred.

Preferably, X is O to 75 and y is 25 to 100
takes the value of

The hydrophilic colloid layer in the photographic light-sensitive material of the present invention has a swelling rate of 300% or less in water, especially 20% by the use of these hardening agents.
It is preferable that the film be hardened to 0 to 270%.

As the support, polyethylene terephthalate film or cellulose triacetate film is preferred.

In order to improve the adhesion with the hydrophilic colloid layer, the surface of the support is preferably subjected to corona discharge treatment, claw discharge treatment, or ultraviolet irradiation treatment, or styrene-butadiene-based latex, vinylidene chloride-based latex, etc. An undercoat layer may be provided, and a gelatin layer may be further provided on top of the undercoat layer.

In addition, an undercoat layer may be provided using an organic solvent containing a polyethylene swelling agent and gelatin.These undercoat layers can be surface-treated to further improve their adhesion to the hydrophilic colloid layer. .

The emulsion layer of the photographic material of the present invention may contain a plasticizer such as a polymer or an emulsion in order to improve pressure characteristics.

For example, British Patent No. 738,618 describes heterocyclic compounds, British Patent No. 738,637 describes alkyl phthalates, British Patent No. 738,639 describes alkyl esters, and U.S. Patent No. 2,960.404 describes polyhydric compounds. Alcohol, 3.1
No. 21,060 contains carboxyalkyl cellulose,
Japanese Patent Application Laid-open No. 495017 discloses a method using paraffin and a carboxylic acid salt, and Japanese Patent Publication No. 53-28086 discloses a method using an alkyl acrylate and an organic acid.

There are no particular restrictions on other structures of the emulsion layer of the silver halide photographic material of the present invention, and various additives may be used as required. For example, Re5search
Disclosurs, Vol. 176, pp. 22-28 (1
Binder surfactant described in December 978),
Other dyes, ultraviolet absorbers, coating aids, thickeners, etc. can also be used.

Hereinafter, the present invention will be specifically explained with reference to Examples.

Example 1 1 ■ 5g of potassium bromide, 0.05g of potassium iodide, 25.0g of gelatin, thioether HO (CHI), S (CHz)z S (CH,) in 1ffi of 2-kyokan water
2.5 cc of a 5% aqueous solution of 20H was added and kept at 69°C, and an aqueous solution of 8.33 g of silver nitrate and an aqueous solution containing 5.94 g of potassium bromide and 726 g of potassium iodide O were added with stirring. It was added in 45 seconds using the double jet method.

Subsequently, after adding 2.5 g of potassium bromide, 8.3 g of silver nitrate was added.
An aqueous solution containing 3 g was added over 26 minutes so that the flow rate at the end of the addition was twice that at the beginning of the addition. 25 more after this
% ammonia solution 20cc, 50%N HaN0
3 After adding 10 cc and physically aging for 20 minutes,
240 cc of N sulfuric acid was added to neutralize it, and then an aqueous solution of 11,153.34 g of nitric acid and an aqueous solution of potassium bromide were added over 40 minutes by a controlled double jet method while maintaining the potential at p, Ag 8.2. The flow rate at this time was accelerated so that the flow rate at the end of addition was nine times the flow rate at the start of addition. After adding W5, add 2N potassium thiocyanate solution 1
Add 5 cc and then add 25 cc of 1% potassium iodide aqueous solution.
was added over 30 seconds. After this, the temperature was lowered to 35°C, soluble salts were removed by the sedimentation method, and then the temperature was lowered to 40°C.
75g of gelatin and 0.7 phenoxyethanol at elevated temperature
Add 3g and adjust the pH to 6.5 with caustic soda and potassium bromide.
0, pAg was adjusted to 8°10.

After raising the temperature to 56° C., 600 μ of a sensitizing dye having the following structure and 150 μ of a stabilizer were added.

After 10 minutes, 2.4 parts of sodium thiosulfate pentahydrate, 140 parts of potassium thiocyanate, and 2.1 g of chloroauric acid were added to the emulsion, and after 80 minutes, it was rapidly cooled and solidified to form an emulsion. In the obtained emulsion, 98% of the total projected area of all grains was composed of grains with an aspect ratio of 3 or more, and the average projected area diameter of all grains with an aspect ratio of 2 or more was 1.051 Im, standard deviation 11°5%. The average thickness was 0.165 μm and the aspect ratio was 6.4.

The following chemicals were added to the emulsion per mole of silver halide to prepare a coating solution.

・Boriaacrylamide (average molecule! 45,000) ・Polymer latex (poly (ethyl acrylate/methacrylic acid) -97/3) ・Hardening agent 1.2-bis (sulfonylua 23.5g 25.0g ・2 ,6-bis(hydroxyamino)-4-diethylamino-1,3,5-)riazine 80 ■ Sodium polyacrylate (average molecular weight 41,000) 4.0 g Potassium polystyrene sulfonate (average molecular weight 600,000) 1.0 g of crossover cut dye 1-1.1-8 was ball milled using the method described in JP-A-63-197943.

・Water 434d and 6.7% aqueous solution of TrlLon X-20OR surfactant (TX-20OR) 791jd
and was placed in a 21 ball mill. 20 g of dye were added to this solution. Zirconium oxide (ZrO) beads 40
(ld (2 m diameter) was added and the contents were ground for 4 days. After this, 160 g of 12.5% gelatin was added. After defoaming, the ZrO beads were removed by filtration. The resulting dye dispersion was When observed, the particle size of the pulverized dye had a wide distribution ranging from 0.05 to 1.15 μm in diameter.

Blue-dyed transparent PET with a thickness of 115 am as a support
A support was used. In order to improve the adhesion with the hydrophilic colloid layer, the surface of the support was previously subjected to corona discharge treatment, and then a first undercoat layer made of styrene-butadiene latex was applied, and a second undercoat layer of 0.08 g/rrf of gelatin was applied on top of the first undercoat layer. Layers were provided.

A fine dispersion of the above dye was coated as a gelatin dispersion solution on both sides of the support in the coating amount shown below. In this way, a crossover cut layer was prepared.

- Gelatin f, 8g/rrl - Dye 1-1 Amount listed in Table-1 - Dye 1
-8 Quantity listed in Table-1 Potassium polystyrene sulfonate (average molecular weight 600,000) 35■/po10■/bo-phenoxyethanol 18ag/rrl
- 1,2-bis(sulfonylacetamido)ethane 100 μ/p Next, the emulsion layer coating solution was coated on both sides of the support coated with the black overcut dye layer at the same time as the surface protection layer coating solution.

The amount of coated silver was 1.80 g/nf (per side).

The surface protective layer was prepared so that each component was coated in the following amounts, and designated as photographic materials 1 to 6 (Table 1).

L-shaped plate 11 Kisei product 1 test 1 gelatin
1.15g/Polyacrylamide (average molecular weight 45,000) 0.25 Sodium polyacrylate (average molecular weight 400,000) 0.02pt
- Sodium salt of octylphenoxy diglyceryl butyl sulfonate 0102・Poly(degree of polymerization 10) Oxyethylene-poly(degree of polymerization 3) Oxyglyceryl-offtyl phenoxy ether O, (+1・CsF
+tSOJ O,OO3sHq Excellent CsH+vSOtN +CH! ÷T-ten CIt z
+a S Os N ao, 001 C3I+?・CeH+, 5OtN +CHtCH*O÷L port +C
Ht CHC11□O+4H0,003 ・Polymethyl methacrylate (average particle size 3.5μm) 0.025・Poly(
Methyl methacrylate/methacrylate) (molar ratio 7:3, average particle size 2゜5μm) 0.020 Easts+an Kodak as a one-plate two-piece fluorescent intensifying screen
MiniR-Fast manufactured by Co., Ltd. was used. Photographic materials 1 to 6 were subjected to X-ray sensitometry using the distance method, and the following treatments (T) to (V) were performed.

Sensitivity is the ratio of the reciprocal of the exposure that gives a density of Fog+1.0, and the combination of photographic material I and processing (1) is 10
Relative display was performed with the value set to 0.

The gradation is Fog+ of the characteristic curve (H&D curve)
It is expressed by the slope of a straight line connecting the density point of 0.25 and the density point of Fog+2.0.

The results are summarized in Table-1.

Measurement of crossover l The percentage of crossover light (%) is as per U.S. Patent No. 4, 8.
03,150. That is, only one side of a photosensitive material having photosensitive layers on both sides is brought into close contact with a fluorescent screen and irradiated with X-rays. The light emitted from the fluorescent screen is absorbed by the adjacent photosensitive layer and dye-colored layer, but some of it is absorbed by the 1
Pass through a 75 μm transparent support to expose the emulsion layer on the opposite side (this phenomenon is called crossover), at this time,
There is a sensitivity difference between the photosensitive layer adjacent to the fluorescent screen and the photosensitive layer on the opposite side. When this sensitivity difference is expressed as ΔLogE, the crossover (%) is crossover (χ') =
It is defined as the antilogous number of X 100 (ΔLog E) +1. At this time, the processing used was the same as the method used to evaluate each image quality and photographic performance. The results are summarized in Table-1.

Note that the ratio of crossover light was constant within the range of experimental error regardless of the processing content.

Automatic processor FRM5000 manufactured by Fuji Photo Film Co., Ltd.
After developing with the following developer (1) at 29° C. for 25 seconds, it was fixed with fixer (1), washed with water, and then dried. D
The dry to dry processing time was 87 seconds.

Soil and 1-phenyl-3-pyrazolidone 1.5g Hydroquinone 3085-Nitroindazole 0.25g Potassium Bromide
3.0g anhydrous sodium sulfite
50g potassium hydroxide 3
0g Boric acid Log Glutaraldehyde 5g Add water to bring the total volume to 11 (pH adjusted to 10.20) Soil and ammonium thiosulfate 140g Sodium sulfite (anhydrous) 20.0g Boric acid
8.0g Ethylenediaminetetraacetic acid disodium di-salt 0.1g Aluminum sulfate 15.0g Sulfuric acid
Add 2.0g glacial acetic acid 22.0g water to 1.02 (pH is 4.20)
Adjust to. ) After developing with the following developer (n), it was fixed with fixer (1), washed with water, and then dried.

Riki Uni L Metol 2゜Sodium Sulfite 100g Hydroquinone
5g Borax・10H202
g Add water and 12 (NaO
The processing time was set as follows by adjusting the rotation speed of the drive motor of the automatic developing machine and the rack lengths for development, fixing, and washing.

Developing at 20°C for 100 seconds Fixing at 20°C for 60 seconds Washing at 15°C for 60 seconds Dry to Dry processing time is 4.
The time was 30 minutes.

Book H-8 Method ■ In the developer (n), change the amount of NaOH and adjust the pH to 1.
It was set at 1,50. The processing time was set according to the following time allocation.

Development: 20°C, 50 seconds fixing, 20°C, 30 seconds washing, 15°C, 25 seconds drying. Dry to dry processing time is 2.
Minutes 45 seconds.

Method ■ Processing was carried out using the following combination of developer (■) and fixer (1).

Niba υ- Metol 2g Sodium sulfite 100g Hydroquinone
15g Borax・10Hz0
Add 2g water
1j1! (Adjusted to pH 10.1 with NaOH) Development: 35°C, 25 seconds fixing, 30°C, 18 seconds washing, 15°C, 12 seconds Dry to dry processing time including drying 88
seconds.

(2) Processing was carried out using the following combination of developer (V) and fixer (1).

Yuu 1AL Jin! L Metol 2g Sodium sulfite 100g Hydroquinone
10g borax・10)(10
2g 5-Nitroindazole 0.08g Glutaraldehyde 4.3g Add water to bring the total amount to 1ffi (pH adjusted to 11.0) Development: 38°C, 18 seconds fixing, 30°C, 11 seconds washing, 20°C, 8 seconds including drying Dry to Dry processing time: 60
seconds.

The chart for MTF measurement was set at 38K using MTF MlniRFast fluorescent screens manufactured by Kodak Co., Ltd. on both sides of the photosensitive material.
Photographic materials 1 to 6 were exposed under X-ray irradiation conditions of VP and 100 mA. Afterwards, perform processing (1) to (V) and MT.
F was measured.

For MTF, see T, H, James km collection "The
Theory of the Photography
ic Process (1977Macsillan)
Company) '592-61B. MTF is 3
Measurement was performed using an aperture of 0 μm×500 μm, and evaluation was performed using a value of a spatial frequency of 3.0 cycles/m. MTF
The evaluation was made on both sides and the portion with an optical density of 0.8.

The above results are summarized in Table-1.

Part 2. Method Using the above photographic materials 1 to 6 and treatments (1) to (V), M
Fan dome imaging was performed as a system using iniRFast fluorescent screens on both sides.

The contents of the fan dome are based on the model of microcalcifications in mammography, and glass beads with a diameter of 0.21 to 0.8M are placed on the back, with a diameter of 0.35mm designed to model the mammary glands.
Added strafted noise using simple nylon wire.

The images thus created were evaluated by a total of 10 people, including 5 X-ray photosensitive material researchers and 5 radiography technicians, and the discrimination ability of the glass beads was compared. Photographic materials 1-6 and processing (1)
A total of 30 images can be created by combining ~(V),
Each evaluator gave them 30 points to 1 point in the order in which they thought the discrimination ability was better (the one with the most points is better).

After the evaluation by the 10 people was completed, the 10 people's points for each image were totaled, and numbers were assigned in descending order of the scores to form a ranking of discrimination ability. The results are summarized in Table-1.

Exposure and development processing (+) to give a density of 1/3 of the sum of the maximum density and Fog density when photographic properties of photographic material 1 are evaluated using processing (1) to (V). This was done for each of (■).

However, after completion of development, the film was not fixed, but was immediately immersed in a 3% acetic acid solution. After the development was sufficiently stopped, it was washed with water and dried in a dark room. After this, gelatin degrading enzyme actinase E
(manufactured by Kaken Pharmaceutical Co., Ltd.), the silver halide particles were taken out, and the developed state of the halogenated root particles was observed using an electron microscope.

The degree of parallel development as used in the present invention is defined by the following equation.

In order to exhibit the effects of the present invention, this value should be at least 1
The number needs to be preferably 3 or more, particularly 10 or more.

The values evaluated in this way are summarized in Table-2.

In addition, when we similarly evaluated photographic materials 2 to 6, there were errors, but the overall trend was that Table 0-2, which was a loser, included this error in Table 2 Table- From the results of No. 1, it is clear that the discrimination ability of the method of the present invention is significantly superior both in terms of the physical property value called MTF and in the sensory evaluation.

In Systems 21 to 24 of the present invention, the gradations were soft and the apparent contrast was low, but the grains were extremely smooth and the outlines of the microbeads were easy to observe. The reason why the ranking of sensory evaluation and MTF is unbeatable is that the gradation is high,
If the MTF is high, the grains will be rough and microsections will be difficult to see, while if the gradation is low, the grains will be smooth but tend to be difficult to distinguish visually due to the lack of contrast. It turns out to be important.

However, in spite of these effects, the degree of discrimination of the present invention is clearly superior to that of the comparative example.

Furthermore, from the results in Table 2, it can be seen that when the development activity is increased and the development processing time is set to 60 seconds or less, the parallel development degree of the present invention increases and the MTF shows a more improved value.

Comparative Example 2 The following dye coating layer was provided on only one side of the support in the same manner as the colored dye layer of Example 1 was prepared.

・Gelatin 3.6g/nf ・Dye 1-1 200■/po ・Dye 1-84
00■/A Potassium polystyrene sulfonate (average molecular weight 600,000) 25■/A Polymethyl methacrylate (average particle size 3.5μm) 25■/A 1,2-
Bis(sulfonylacetamido)ethane 200 cm/h On the opposite side of the support from the dye-colored layer, the emulsion layer and surface protective layer of Example 1 were coated by coextrusion.

However, at this time, only the flow rate of the emulsion layer was twice that of Example 1, so that the amount of silver coated on one side was 3.6 g/nf.

In this way, one-sided photosensitive photographic material 7 was obtained.

Image quality as a single-sided system was evaluated using Photographic Material 7 and fluorescent intensifying screen Mini RFast.

The results are summarized in Table 3. Incidentally, the sensitivity was displayed so that a relative comparison with Example-1 could be made.

Although there were individual differences in sensory evaluation, system 1 to Example 1
When compared with 30, the result was Q~[phase].

By comparing Table 3 with Table 1, it can be seen that the system of the present invention has significantly higher sensitivity than the conventional single-sided system, and is also superior in discrimination ability.

The present invention reduces the patient's exposure dose to less than half that of conventional manual diagnostic systems and provides highly sharp images.

Example 3 A blue-colored polyethylene terephthalate base having a thickness of 175 μm was provided with an undercoat layer on both sides at the following coating amount per side.

・Gelatin 180■/IH%C Mushroom Js 200■/Pony base with the emulsion of Example 1 applied at a coating silver amount of 1. At this time, apply it to both sides so that it is 9g/rrf.
The same coating as in Example 1 was used for the surface protective layer. The amount of hardener added is 10smol/:)Og-gej! It was changed to In this way, photographic image 8 was obtained. Evaluation was performed using the same method as in Example 1.

The results are summarized in Table 4. Sensitivity is expressed in percentages to enable relative comparison with Example 1.2.

From the results shown in Table 4, it is clear that the effects of the present invention are fully exhibited even when anionic dyes are immobilized using cationic latex as a mordant.

Example 4 Crossover Cut Dyes 1 to 1 and I-8 were ball milled in the same manner as in Example 1 to obtain a fine dye dispersion having a diameter of 0.05 to 1.15 μm.

Each dye dispersion was centrifuged to precipitate coarse particles, and the supernatant liquid was collected.

The resulting dye was an ultrafine dye dispersion with a particle size ranging from 0.05 to 0.15 μm.

Transparent PET dyed blue with a thickness of 175 μm as a support
A support was prepared. In order to improve the adhesion to the hydrophilic colloid layer of the support, the surface was previously subjected to corona discharge treatment, and then a first undercoat layer made of styrene-butadiene latex was provided on both sides.

On top of this, a second gelatin undercoat layer having the following composition was coated on both sides.

Atano・Gelatin 0.25g/Po・Dye■
Ultrafine dispersion of 80■/rd Ultrafine dispersion of dye H 160■/rrf8 cut into 4 pieces (
Each photosensitive material was cut into pieces of 24×30C11) and subjected to continuous processing.

The results are summarized in Table-5.

LoI 1 g/rrl In exactly the same manner as in Example 1, an emulsion layer and a surface protective layer were coated on a support coated with the above-mentioned undercoat layer.

Photographic material 9 was thus obtained.

■'s and's.

Process (V) of Example 1 was carried out under drying conditions such that the drying air temperature was 50° C. and the residence time of the photosensitive material in the drying zone was 10 seconds.

From the results of Photographic Material 5 of Example 1 and Photographic Material Table 5 of this Example, the method of the present invention in which an ultrafine dye dispersion is applied to an undercoat layer to form a crossover cut colored layer is
In this embodiment, which has an ultra-high image quality of 60 seconds to dry and ultra-quick processing, it is excellent in terms of sharpness, sensitivity, and drying performance in continuous processing, and is the most preferred embodiment of the present invention. It can be seen that it is.

Example 5 1M ■Sarakesui 1! Potassium bromide 5g 1 gelatin 20g 1 thioether HO (CHI) (CHz)xs (CH 10
A solution containing 8.33 g of silver nitrate, 5.94 g of potassium bromide, and 0.726 g of potassium iodide was added to a container containing 2.5 cc of a 5% aqueous solution of H and kept at 65°C while stirring. The mixture was added by a jet method over a period of 45 seconds, followed by the addition of 2.7 g of potassium bromide, and then an aqueous solution containing 8.33 g of nitric acid over a period of 14 minutes. 25% after this
20 cc of ammonia aqueous solution, 50% NHa NOs
After adding 10cc and physically aging for 20 minutes, IN
240 cc of sulfuric acid was added to neutralize.

Subsequently, an aqueous solution of 153.34 g of silver nitrate and a mixed aqueous solution of potassium bromide and potassium iodide were added over 45 minutes by a controlled double jet method while maintaining the potential at p/Ig 8.05. The flow rate at this time was accelerated so that the flow rate at the end of addition was eight times that at the start of addition. The amount of potassium iodide added in this control double jet was 12 g as Kl.

After the addition was complete, 30 cc of 2N potassium thiocyanate solution was added. After that, the temperature was lowered to 35°C, soluble salts were removed by the sedimentation method, and then the temperature was raised to 40°C to remove gelatin.
0g and phenoxyethanol 0.7g, Na
pH 6.85, PAg 8.0 by OH and potassium bromide. Adjusted to O. After raising the temperature to 65°C, 65 omg of the sensitizing dye of Example 1 and 300 μg of silver halide stabilizer were added.

After 10 minutes, 3 parts of sodium thiosulfate pentahydrate, 140 mg of potassium thiocyanate, and 2.5 parts of chloroauric acid were added, and after 10 minutes, the mixture was cooled to form an emulsion.

The resulting emulsion had an average projected area diameter of 1.16 μm, a standard deviation of 16.8%, an average thickness of 0.171 μm, and an aspect ratio of 6.8.

Thereafter, chemicals were added in the same manner as in Example 1 to complete an emulsion coating solution.

A support coated with an ultrafine dye dispersion on the undercoat layer was prepared in the same manner as prepared in Example 4.

The above-mentioned emulsion coating solution and the same surface protective layer as in Example 1 were coated on both sides of this support.

The amount of silver coated was 2.0 g/nf per side.

Photographic material 10 was thus obtained.

blood dish shin Various performances were evaluated in the treatment (I) of Example-1.

The results are summarized in Table-6.

From the results in Table 6, it can be seen that the system Nα38 also has the features of the present invention of high sensitivity and ultra-high sharpness.

When the silver halide composition is increased as in Photographic Material 10 (AgBr I: Ag I content: 17.67 mol %), even processing agents that were not conventionally used for parallel type development, such as processing H), can be used with the parallel type development of the present invention. (parallelfashio
It can be seen that n) can be realized.

Patent applicant: Fuji Photo Film Co., Ltd. Procedural amendment 4. Subject of correction “Detailed description of the invention” in the specification column Heisei 1 July Day

Claims (2)

[Claims] (1) In an X-ray image forming method for developing a medical photographic material having at least one photosensitive silver halide emulsion layer on each side of a transparent support, the cross-over light of the photographic material is 12% or less. An X-ray image forming method characterized in that the development progress state of the silver halide emulsion is parallel development. (2) The X-ray image forming method according to claim 1, wherein the developing time is 60 seconds or less.