JPH02124565A - Positive type image forming method - Google Patents

Abstract

PURPOSE:To prevent a silver image from being tinged with yellow by exposing and developing a prefogged autopositive photosensitive material contg. a silver halide emulsion having 0.21-0.40mum average particle size and 2.1-3.4g/m<2> amt. of silver applied so as to attain 2.7-4.0 max. density. CONSTITUTION:A prefogged direct positive silver halide photosensitive material contg. a silver halide emulsion having 0.21-0.4mum, preferably 0.22-0.38mum average particle size and 2.1-3.4g/m<2>, preferably 2.2-3.3g/m<2> amt. of silver applied is exposed and developed so as to attain 2.7-4.0 max. density Dm. The silver halide emulsion used is preferably a single displayed silver halide emulsion. A formed silver image can be prevented from being tinged with yellow.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a pre-foamed direct positive photosensitive material, which can be processed by conventional Dry to D using an automatic processor.
The present invention relates to a silver halide photographic light-sensitive material that has excellent suitability for not only ry 90 second processing (RP 90 second processing) but also recently developed ultra-rapid processing, and a positive image forming method using the same.

(Background of the Invention) Ultra-quick processing of medical photographic materials is in demand in the market. Accordingly, there is a desire for ultra-quick processing of duplex sensitive materials.

If conventional RP 90 seconds processed sensitive material is processed ultra-quickly, it will suffer from insufficient maximum density (Dm), sensitivity, gradation, etc. due to development delay.
It cannot be used due to large Dm fluctuations, delayed fixing, poor drying, etc.

Recently developed ultra-rapid treatments (eg Dryt).

There are two types of developing solutions (Dry for 50 seconds or less) that contain a processing hardener and those that do not. As processing methods in the market change, sensitive materials that are suitable for image processing are required. There is a need for a duplex sensitive material that is suitable not only for the conventional 90-second RP processing but also for the newly developed ultra-rapid processing in which the developer contains a hardening agent or in which the developer does not contain a hardening agent.

(Problems to be Solved by the Invention) The object of the present invention is to provide a silver image that is suitable for not only conventional RP processing but also ultra-rapid processing that contains a hardening agent in the developer and ultra-rapid processing that does not contain a hardening agent. It is an object of the present invention to provide a photosensitive material for duplication that does not give off a taste and allows stable film position detection using LEDs.

(Means for solving the problem) In order to make the emulsion suitable for ultra-rapid processing, the emulsion crystal grains are made small, and the required amount of coated emulsion (corresponding to the amount of coated silver) is reduced by making use of rapid development progress and high covering power. The objective is to reduce the development progress rate to an initial rapid type, and to saturate the development during a short development time.

Furthermore, the degree of hardening of the coating film is increased to reduce the drying load after processing, but particles with small particle size are advantageous because the decrease in covering power is relatively small as the degree of hardening increases. However, when the particle size is reduced, the color of the silver image becomes yellowish and the visual contrast decreases, making diagnosis difficult. Furthermore, if the particles are small and the amount of silver coated is low, the transmittance in the infrared region will be large, making detection by LED film using light around 950 nm unstable. Next, when the particle size is increased, the variation in the reduction and increase in covering power becomes larger depending on the presence or absence of development hardening, and it is possible to obtain substantially the same characteristic curves in both development hardening and non-development hardening processes. become unable to do so.

The Dm of various originals used for duplex is 2°7~4
．． It is often at 0. In order to faithfully reproduce these originals, it is essential that the duplex sensitive material has a Dm of 2.7 to 4.0. It is preferable that the average gradation is around 1, but people have different preferences, and a certain degree of rj+ is allowed.

In order to solve these problems, as a result of intensive research, the average grain size of the silver halide emulsion is 0.21 to 0.4 μm, preferably 0.22 to 0.38 μm, and the amount of coated silver is 2.1 μm. ~3.4g/rd preferably 2.2-3.3g
By exposing and developing a pre-fogged direct positive silver halide photosensitive material of /m, the maximum density (Dm) is 2.7.
It has been found that the object of the present invention can be achieved by an image forming method that provides a viscosity of 4.0 to 4.0.

The silver halide emulsion used in the present invention may be monodisperse or polydisperse, but monodisperse is preferable.

Furthermore, two or more types of monodispersed emulsions having different particle sizes may be used in combination as described in Japanese Patent Application No. 61230428. Furthermore, two or more types of monodisperse emulsions having different sensitivities may be used in combination.

Two or more emulsions may be applied in two or more layers. In this case, it is preferable to coat the highly sensitive emulsion on a side farther away from the support.

In the present invention, a plurality of silver halide emulsions can be divided into a plurality of layers and used in this way, but the total average grain size of all emulsions is 0.21 to 0.4.
．． 0 μm, coating silver amount is 2.1 to 3.4 g/rd, and D
It is necessary that m is 2.7 to 4.0.

(100) plane/(111) that can be used in the present invention
Monodisperse silver halide emulsion grains with one or more solidifications can be prepared by various methods.

The most common method is to keep the pAg value during grain formation at a constant value of 8°10 or less and simultaneously add a silver nitrate aqueous solution and an alkali halide aqueous solution at a rate that is faster than the dissolution rate of the particles and does not cause large re-nucleation. (so-called controlled double jet method). More preferably pAg
The value is 7.80 or less, more preferably I) Ag value is 7.6.
It is better to set it to 0 or less. When silver halide grain formation is divided into two processes: nucleation and growth, the pAg value during growth is preferably 8.10 or less, more preferably 7.80.
Below, it is more preferable to set it as 7.60 or less. Although the soluble silver salt and the soluble halogen salt may be reacted by a one-sided mixing method, a simultaneous mixing method is preferred in order to obtain good monodispersity.

The silver halide emulsion used in the present invention preferably contains 5 Qwt% or more of silver halide grains with (100) plane/(111) solidification of 1 or more, preferably 2 or more, more preferably 4 or more. , more preferably 60 wt% or more, particularly preferably 8 Qwt% or more.

The photosensitive silver halide used in the present invention includes, for example, silver bromide,
Any silver halide consisting of chlorine, bromine, or iodide, such as silver iodobromide, silver chloride, silver chlorobromide, silver chloroiodide, silver chloroiobromide, etc., may be used, but silver bromide, silver iodobromide, etc. Silver oxide and silver chloroiodobromide are preferred. Silver iodide in the silver halide is preferably 0 to 4 mol%, particularly preferably 0 to 2 mol%. The amount of silver chloride in the halogenated eye is preferably at most 40 mol% or less, more preferably at least 20 mol% or less, and particularly preferably 10 mol% or less.

These emulsions may have coarse grains, fine grains, or a mixture thereof, but preferably have an average grain size of about 0 (as measured by the projecting area method or number average method).
．． Emulsion grains of 21 microns to 0.40 microns are preferred. The particle shape is preferably cubic, but as long as it satisfies the surface index conditions of the present invention, it may be potato-shaped, spherical, plate-shaped, or tabular with a particle diameter of 5 times or more the particle thickness (for details, see Research Disclosure (RESERCHDISCLO)).
3URE) Item 1lh22534p, 20~p
, 58 (described in January 1983) may have an irregular crystal form. These light-sensitive emulsions may be mixed with a substantially non-light-sensitive emulsion (for example, an internally fogged fine grain emulsion). Of course, it may be used by coating in separate layers.

Furthermore, even if the crystal structure of the silver halide grains is similar up to the inside, there are also grains with a layered structure with different interior and exterior structures, British Patent Section 635.84.1, and U.S. Patent No. 3.6.
It may also be of a so-called conversion type as described in No. 22,318.

Incorporation of iridium ions is achieved by adding a water-soluble iridium compound (for example, hexachloroiridate (III) salt or hexachloroiridate (IV) salt) in the form of an aqueous solution during the preparation of the silver halide emulsion. let It may be added in the same aqueous solution as the halide for grain formation, it may be added before grain formation, it may be added during grain formation, or it may be added after grain formation until fogging, but it is preferable to add it. is added during particle formation. Particularly preferred is embedding inside the particles.

In the present invention, to increase the sensitivity of the emulsion, it is necessary to use 10-7 to 10-3 mol of iridium ion per mol of silver halide, preferably 5 x 10-7 to 5
X 10-' mole.

During the formation of silver halide grains, silver halide solvents such as ammonia, rhodanpotash, rhodanammonium, thioether compounds (e.g., U.S. Pat. No. 3,271.157, U.S. Pat.
No. 574,628, No. 3,704,130, No. 4
．． 297. No. 439, No. 4,276.374,
etc.) 1,000-ion compounds (e.g., JP-A-53-144319
No. 53-82408, No. 55-77737, etc.), amine compounds (e.g. JP-A No. 54-10071)
No. 7) etc. can be used.

In addition to silver halide solvents, compounds that control crystal habit by adsorbing onto the grain surfaces, such as cyanine dyes, tetrazaindene compounds, and mercapto compounds, can be used during grain formation.

The ratio of (100) planes to (111) planes of particles can be determined by the Herkamunk dye adsorption method (hereinafter referred to as the "Kuchelkamunk method"). This method preferentially adsorbs to either the (100) or (111) plane, and
A dye is selected in which the association state of the dye on the 100) plane and the association state of the dye on the (111) plane are spectrally different. The (100) plane/(111) plane ratio can be determined by adding such a dye to an emulsion and examining the spectra in detail with respect to the amount of the dye added.

Fog can be applied to the direct positive type silver halide used in the present invention by a conventionally known technique after water-soluble salts generated after precipitation of the silver halide are removed. Fog can be imparted by using a fogging agent (reducing agent) alone or by combining the fogging agent with a gold compound or a useful metal compound that is more electrically positive than silver. Alternatively, the light may be provided by a combination of metal compounds.

Representative fogging agents useful in making such emulsions include, for example, formalin, hydrazine, polyamines (triethylenetetramine, tetraethylenepentamine, etc.), thiourea dioxide, tetra(hydroxymethyl)phosphonium chloride, acineborane hydrogenation. Contains boron compounds, stannous chloride, tin (II) chloride, etc.
Typical useful metal compounds that are more electrically positive than silver include soluble salts of gold, rhodium, platinum, palladium, iridium, etc., such as potassium chloroaurate, chloroauric acid, palladium ammonium chloride, Included are sodium iridium and the like.

The fogging agent is generally 1.0X per mole of silver halide.
It is used in a range of 10-' to 1.0×10-' moles.

Typical gold compounds include chloroauric acid, sodium chloroaurate, sulfur compounds, selenium compounds, etc., and are generally 1.0X10-6 to 1.0X10-' per mole of silver halide.
It is preferable to contain it in a molar range.

The degree of fogging of the prefogged direct positive silver halide emulsions used in the present invention can be varied over a wide range. The degree of fogging depends on the silver halide composition, grain size, etc. of the silver halide emulsion used, the type and concentration of the fogging agent used, and the point at which fogging is applied, as known by those skilled in the art. The pH of the emulsion of HlpAg, /
It is related to IA degree and opening time.

The direct positive silver halide used in the present invention contains an inorganic desensitizer (i.e., noble metal atoms such as iridium and rhodium contained in silver halide grains) and an organic desensitizer adsorbed on the silver halide surface, either singly or in combination. It can be contained in combination.

Examples of organic desensitizers that can be used in the present invention include dimethine cyanine dyes containing a 2-toro-substituted phenyl)-indole nucleus, and bis-(1 alkyl-2-phenyl)-indole-3 trimethine cyanine dyes. , cyanine dye containing an aromatic substituted indole nucleus, imidazoquinoxaline dye, asymmetric cyanine dye containing a carbazole nucleus, 2
trimethine cyanine dyes containing an aromatic substituted indole nucleus, cyanine dyes containing a l-13-)realkyl-3H-nitroindole nucleus, cyanine dyes containing a complex fused pyrimidinedione nucleus, 2-isoxazoline-5
- quaternized merocyanine dyes with one nucleus, 2-pyrazolin-5-one nucleus or complex fused pyrimidinedione nucleus, 2-allylimino (or alkylimino)
cyanine dyes containing -4 allyl (or alkyl)-3-thiazoline nuclei, merocyanine quaternary ammonium salt dyes having 3-allyl-amino or 3-lower fatty acid amide-substituted 2-pyrazolin-5-ones, biryllium, thiapyrylium, Selenapyryllium salt dyes, cyanine dyes having a 21-ro-substituted 2-arylindole nucleus, bipyridinium salt dyes, cyanine dyes containing a pyrrole nucleus bonded at the 2-position carbon atom, 1,2-diaryltrimethine indole dyes, A cyanine dye containing a 4-pyrazole nucleus, a polymethine dye containing an imidazole nucleus, a dimethine cyanine dye containing a 2-phenyl-substituted indole nucleus, a trimethine cyanine dye consisting of two indole nuclei, a 1-cyanoalkyl-2-arylindole nucleus cyanine dyes containing, cyanine and merocyanine dyes in which two nuclei have desensitizing substituents such as nitro groups, cyanine dyes containing l-furkyl-2-phenyl substituted indole nuclei, containing 1-alkoxy-2-arylindole nuclei; Cyanine dye, cyanine dye having an imidazo(4,5,6)quinoxaline nucleus, dye containing a cyclohebutanetriene ring, dimethine cyanine dye containing an indole nucleus, dimethine cyanine dye containing a (2,1-b) pyridine nucleus , cyanine dyes containing a pyrrole nucleus, dyes containing a pyrrolo(2,1-b)thiazole nucleus, benzoyl or phenylsulfonyl't substituted Is
Cyanine dyes containing indole or indolenine nuclei Nitrostyryl-type compounds described in U.S. Pat. -8746, a dimethine cyanine dye containing a pyrazolobenzimidazole nucleus, such as 3-ethyl-2
-[2(1,2-dimethylbenzimidazo(2,1-e
)3-pyrazolin-3-yl)vinyl]penzothiazolium broside, dimethine cyanine dyes with a pyrazoquinazolone nucleus, e.g. 5-ethoxycarbonyl-1,
3,3-1-dimethyl-2-(1-(2,4-dimethyl-9-oxovirazolo(5,1-b)quinazoline-3-
yl)vinyl]3f eindolium-4methylhenzosulfonate, 3-ethyl-2-(2-(2,4-dimethyl-9-oxopyrazolo(5,1-b)quinazoline-
3-yl)vinyl]benzothiazolium 4-methylhenzenesulfonate and the like are useful.

In addition, the compound represented by - Tsuzuriyo (1) (■ (1-2),
(I-3) is also useful.

(T) and in the formula, Zl represents a nonmetallic atomic group necessary to form a nitrogen-containing heterocycle.

T is an alkyl group, cycloalkyl group, alkenyl group, halogen atom, cyan group, trifluoromethyl group, alkoxy group, aryloxy group, hydroxy group, alkoxycarbonyl group, carboxyl group, carbamoyl group, sulfamoyl group, aryl group, acylamino group, a sulfonamide group, a sulfo group, or a Henzo-fused ring, which may further have a substituent.

q is 1.2 or 3 r represents 0.1 or 2.

In general formula (1), specific examples of the nitrogen-containing heterocycle completed by (c) include 1.2.4-) lyazole ring, 1,3.4-oxadiazole ring, 1,3.4- Thiadiazole ring, tetraazaindene ring, pentaazaindene ring, triazaindene ring, benzothiazole ring,
Benzimidazole ring, benzoxazole ring, pyrimidine ring, triazine ring, pyridine ring, quinoline ring, quinazoline ring, phthalazine ring, quinoxaline ring, imidazo [
4,5-β]quinoxaline ring, tetrazole ring, I, 3
-diazabrene ring, etc., and these rings may further have a substituent or may be further fused.

- Specific examples of compounds represented by <1) (■ (■ (I)
It is preferably added in an amount of from 5 x 10-' mol to 1 x 10-' mol, particularly from 1 x 10-' mol to 2 x 10-' mol.

When these compounds are incorporated into photographic materials, water-soluble compounds may be incorporated into aqueous solutions; water-insoluble compounds may include alcohols (e.g. methanol, ethanol), esters (
It may be added to a silver halide emulsion solution or a hydrophilic colloid solution as a solution of a water-miscible organic solvent such as ethyl acetate) or ketones (eg acetone).

When added to a silver halide emulsion solution, it can be added at any time from the start of fogging until coating, but it is preferably added after fogging, especially when the coating is prepared for coating. It is preferable to add it to the liquid.

The direct positive silver halide photographic light-sensitive material of the present invention contains a selenium compound as described in JP-A No. 46-4282, and a sensitizing dye such as a dimethine trimethine cyanine dye, a halogen-substituted hydroxyphthalein dye, Phenazine dyes, benzothiazole, cyanine dyes containing a henzoselenazole nucleus, cyanine dyes containing a naphthoxazole nucleus, triphenylmethane dyes, cyanine dyes containing an indolenine nucleus, cyanine dyes containing a 2-pyridine-rhodanine nucleus, thiazole Cyanine pigment containing nucleus,
High sensitivity can be provided by containing a substance such as at least one dye selected from asymmetric cyanine, quinoline, meso-substituted cyanine dye, cyanine dye containing a rhodanine nucleus, and polymethine dye having three nuclei. .

The direct positive silver halide photographic material of the present invention may contain various other commonly used photographic additives. As stabilizers, for example, triazoles, azaindenes, quaternary henzothiazolium compounds, mercapto compounds, or cadmium, cobalt, nickel,
Water-soluble inorganic salts such as manganese, gold, thallium, and zinc may also be contained. Also, as a hardening agent, for example, formalin,
Aldehydes such as glyoxal and mucochloric acid, S-
) Lyazines, epoxies, aziridines, vinyl sulfonic acid, etc. Also contains coating aids such as saponin, sodium polyalkylene sulfonate, lauryl or oleyl monoether of polyethylene glycol, amylated alkyl taurine, fluorine-containing compounds, etc. You can force it. Furthermore, it is also possible to contain a color coupler. Other whitening agents, ultraviolet absorbers, preservatives, etc. as necessary.
A capping agent, an antistatic agent, etc. can also be contained.

Further, the direct positive silver halide photographic light-sensitive material of the present invention contains a so-called filter dye, which absorbs and cuts visible light so that it can be handled under a fluorescent lamp that cuts off ultraviolet light using an ultraviolet light source. I can do it.

The dye used in the present invention has a main absorption in the visible wavelength range of the wavelength range of inherent sensitivity of the silver halide emulsion used. Among them, λmax is 350 nm to 600
Dyes in the nm range are preferred. There are no special restrictions on the chemical structure of the dye, and oxonol dyes, hemioxonol dyes, merocyanine dyes, cyanine dyes, ab dyes, etc. can be used, but water-soluble dyes are useful in terms of eliminating residual color after processing. It is.

Specifically, for example, pyrazolone dyes described in Japanese Patent Publication No. 58-12576, pyrazolone oxonol dyes described in U.S. Pat. No. 2,274°782, and U.S. Pat. No. 2,956
, 879, U.S. Pat.
．． 4.23,207, the styryl dyes and butadienyl dyes described in U.S. Patent No. 3,384,487, and U.S. Pat.
Merocyanine dyes described in US Pat. No. 3,486,897 and US Pat. No. 3,652,284,
merocyanine dyes and oxonol dyes described in U.S. Patent No. 3,718,472, enamine hemioxonol dyes described in U.S. Pat.
No. 84.609, No. 1,177.429, JP-A-4
No. 8-85130, No. 49-99620, No. 4!11
14420, U.S. Patent No. 2.533.472, U.S. Patent No. 3,148.187, U.S. Pat.
The dyes described in Patent No. 3,575,704 and Patent No. 3,653,905 are used.

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, adhesion prevention, and photographic property improvement (e.g.
Various surfactants may be included for various purposes such as development acceleration, high contrast, and sensitization.

For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol alkyl ethers, polyalkylene glycols Nonionic surfactants such as alkylamines or amides, polyethylene oxide adducts of silicone), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Agents; alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfonate Anionic surfactants containing acidic groups such as carboxy groups, sulfo groups, phosphoro-sulfate groups, and phosphate groups, such as alkyl polyoxyethylene alkyl phenyl ethers and polyoxyethylene alkyl phosphates; amino acids amphoteric surfactants such as aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphoric acid esters, alkyl betaines, amine oxides; alkylamine salts, aliphatic or aromatic quaternary ammonium salts, pyridinium,
Cationic surfactants such as phosphonium or sulfonium salts containing heterocycles, such as imidabriram, quaternary ammonium salts, and aliphatic or heterocycles can be used.

In particular, surfactants preferably used in the present invention are polyalkylene oxides having a molecular weight of 600 or more described in Japanese Patent Publication No. 58-9412.

The polyalkylene oxide compound used in the present invention consists of at least 10 units of alkylene oxide having 2 to 4 carbon atoms, such as ethylene oxide, propylene-1,2 oxide, butylene-1,2-oxide, and preferably ethylene oxide. Condensates of polyalkylene oxides and compounds having at least one active hydrogen atom such as water, aliphatic alcohols, aromatic alcohols, fatty acids, organic amines, hexitol derivatives, etc., or block copolymers of two or more types of polyalkylene oxides, etc. includes.

When these polyalkylene oxide compounds are added to a silver halide emulsion, they are dissolved in an aqueous solution of an appropriate concentration or in a low boiling point organic solvent that is miscible with water.
It can be added to the emulsion at any suitable time before coating, preferably after chemical ripening. It may be added to non-photosensitive hydrophilic colloid layers, such as intermediate layers, protective layers, filter layers, etc., instead of being added to the emulsion.

The photographic emulsion of the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability. For example, alkyl (meth)acrylates, alkoxyalkyl (meth)acrylates, (meth)acrylamides, vinyl esters (e.g. vinyl acetate),
Acrylonitrile and the like can be used alone or in combination.

The emulsion used in the present invention mainly uses gelatin as a protective colloid, and it is particularly advantageous to use inert gelatin. Instead of gelatin, photographically inert gelatin derivatives (such as phthalated gelatin), water-soluble synthetic polymers such as polyvinyl acrylate, polyvinyl alcohol, polyvinylpyrrolidone, dextran, polyacrylamide, etc. are used.

Polyols such as trimethylolpropane, bentanediol, butanediol, ethylene glycol, and glycerin can be used as plasticizers.

The novel emulsions of the present invention can be applied to any suitable photographic support, such as glass, film bases such as cellulose acetate, cellulose acetate butyrate, polyester [
For example, poly(ethylene terephthalate) is used. In particular, it is preferably colored blue.

The surface of the support is preferably subjected to corona discharge treatment, glow discharge treatment, or ultraviolet irradiation treatment in order to improve adhesion to the hydrophilic colloid layer. Alternatively, an undercoat layer made of styrene-butadiene latex, vinylidene chloride latex, etc. may be provided.
A gelatin layer may be further provided on top of the gelatin layer.

Further, 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 silver halide photographic light-sensitive material of the present invention contains a developing agent such as hydroquinones; catechols; aminophenols; 3-virapritones; ascorbic acid and its derivatives; reductones and phenylenediamines; Combinations of active ingredients can be included. The developing agent can be incorporated into the silver halide emulsion layer and/or other photographic layers (eg, protective layers, interlayers, filter layers, antihalation layers, bank layers, etc.).

The developing agent may be dissolved in a suitable solvent or as described in U.S. Pat.
, 592,368 and French Patent No. 1,505.778.
It can be added in the form of a dispersion as described in No.

In the present invention, US Pat. No. 2992.1
No. 01, No. 2,701,245, No. 4.142,89
Homopolymer of polymethyl methacrylate or polymer of methyl methacrylate and methacrylic acid as described in No. 4, No. 4,396,706, organic compounds such as starch, silica, titanium dioxide, sulfuric acid, strontium,
Fine particles of an inorganic compound such as barium can be used. The particle size is 1.0 to 10 μm, especially 2 to 5 μm.
It is preferable that it is m.

The surface layer of the photographic light-sensitive material of the present invention contains silicone compounds described in U.S. Pat. No. 3,489,576 and U.S. Pat. In addition, paraffin wax, higher fatty acid esters, starch derivatives, etc. can be used.

Any known method can be used for photographic processing of the light-sensitive material produced by applying the present invention.

A known treatment liquid can be used. The processing temperature is usually chosen between 18°C and 50°C.

Development processing to form silver images depending on the purpose (black and white photographic processing)
Alternatively, any color photographic process consisting of a development process to form a dye image can be applied.

For details, see Research Disclosure Volume 176 1
IkL17643, pages 28-29, Volume 187, 1Ik
It can be developed by the method described in the left column and right column of page 651 of 1+8716.

In the ultra-rapid processing of the present invention, it is preferred that the emulsion layer and/or other hydrophilic colloid layers contain organic substances that would flow out during the development process. When the substance to be discharged is gelatin, it is preferable to use a gelatin species that is not involved in the crosslinking reaction of gelatin by a hardening agent, such as acetylated gelatin or phthalated gelatin, and preferably has a small molecular weight. On the other hand, as a polymer substance other than gelatin, U.S. Patent No. 3,271°15
Polyacrylamide as described in No. 8, or hydrophilic polymers such as polyvinyl alcohol and polyvinylpyrrolidone can be effectively used, and saccharides such as dextran, sucker rose, pullulan, etc. are also effective. Among these, polyacrylamide and dextran are preferred, and polyacrylamide is a particularly preferred substance.

The average molecular weight of these substances is preferably 20,000 or less, more preferably 10,000 or less.

The combination of dihydroxybenzenes and 1-phenyl-3-virapritones is most preferable as the developing agent used in the black and white developer used in the development process of the present invention, since it is easy to obtain good performance. Of course, a p-aminophenol type developing agent may also be included.

The dihydroxybenzene developing agents used in the present invention include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5
Examples include -dichlorohydroquinone, 2,3-dibromohydroquinone, and 2.5-dimethylhydroquinone, with hydroquinone being particularly preferred.

Examples of the p-aminophenol developing agent used in the present invention include N-methyl-p-aminophenol, p-aminophenol, N-(β-hydroxyconityl)-p-aminophenol, and N-(4-hydroxyphenyl). There are glycine, 2-methyl-p-aminephenol, p-hendylaminophenol, among others, N~methyl-p-
Aminophenols are preferred.

The 3-pyrazolidone developing agent used in the present invention is l
-phenyl-3-virapriton, 1-phenyl-4,4
-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-
Phenyl-4,4 dihydroxymethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-virapritone, 1
~ p-aminophenyl-4,4-dimethyl-3-pyrazolidone, 1-p-tolyl-4,4-dimethyl-3-pyrazolidone, t-p-tolyl-4-methyl 4-hydroxymethyl-3-pyrazolidone, etc. be.

The developing agent is preferably used in an amount of usually 0.01 mol/l to 1.2 mol/l.

Sulfite preservatives used in the development process of the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and the like. The amount of sulfite is preferably 0.2 mol/1 or more, particularly 0.4 mol/1 or more. Also, the upper limit is 2.
Preferably, the amount is up to 5 mol/a.

The pH of the developer used in the development process of the present invention is preferably in the range of 9 to 13. More preferably, the pH range is from 10 to 12.

Alkaline agents used to set pH include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, trisodium phosphate, and potassium triphosphate.
Contains H regulator.

Japanese Patent Application No. 1987-28708 (Borate), Japanese Patent Application No. 1988-
Buffers such as No. 93433 (eg, zasocalose, acetoxime, 5-sulfosalcylic acid), phosphates, carbonates, etc. may also be used.

Further, dialdehyde hardeners or bisulfite adducts thereof may be used in the developer, and specific examples thereof include glutaraldehyde and bisulfite adducts thereof.

Additives used in addition to the above components include development inhibitors such as sodium bromide, potassium bromide, and potassium iodide:
Organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, ethanol, methanol: 1-phenyl-5-mercaptotetrazole, 2-mercaptohenraimidazole-5-sulfonic acid sodium salt, etc. It may also contain antifoggants such as mercapto compounds, indazole compounds such as 5-nitroindazole, and penttriazole compounds such as 5-methylbenztriazole. Foaming agent, water softener, JP-A-56-
It may also contain the amino compounds described in No. 106244.

In the development process of the present invention, a silver stain preventive agent, such as the compound described in JP-A-56-24347, can be used in the developer.

In the developer of the present invention, amino compounds such as alkanolamines described in JP-A-56-106244 can be used.

In addition, "Photographic Processing Chemistry" by F. and A. Mason, published by Focal Press (
1966), pp. 226-229, U.S. Patent No. 2,19
No. 3,015, No. 2.592364, Japanese Unexamined Patent Publication No. 1973-6
4.933 may be used.

The fixer is an aqueous solution containing thiosulfate and has a pH of 3.8 or higher, preferably 4.2 to 7.0.

More preferably the pH is 4.5 to 5.5.

Examples of the fixing agent include sodium thiosulfate and ammonium thiosulfate, and ammonium thiosulfate is particularly preferred from the viewpoint of fixing speed. The amount of fixing agent used can be changed as appropriate, and is generally about 0. 1 to about 6 mol/p.

The fixer may also contain water-soluble aluminum salts that act as hardeners, such as aluminum chloride, aluminum sulfate, potassium alum, and the like.

In the fixing solution, tartaric acid, citric acid, gluconic acid, or their derivatives can be used alone or in combination of two or more. These compounds have a constant s'a1p of 0
．． 0.01 mole/p to 0.03 mole/l is particularly effective.

The fixing solution may optionally contain preservatives (e.g. sulfites, bisulfites), pH buffering agents (e.g. acetic acid, boric acid), p.
It can contain an H adjuster (for example, sulfuric acid), a chelating agent with water softening ability, and a compound described in Japanese Patent Application No. 60-218562.

For the ultra-rapid processing of the present invention, it is preferable to reduce the oil swelling percentage of the light-sensitive material (preferably 100% to 200%) and to reduce the extent of the processing hardening film. That is, it is better to take advantage of the hardening effect during development, and also take advantage of the hardening effect during fixing. To achieve this, it is necessary to lower the degree of swelling of the photosensitive material. The pH of the fixing solution may be set to 4.6 or higher to weaken the hardening reaction, or a fixing solution without a hardening agent is preferable.

In the above-mentioned method for developing a silver halide photographic light-sensitive material of the present invention, after the development and fixing steps, 31
It is also possible to perform treatment with water washing or stabilizing liquid at the following replenishment amounts (including 0, ie, reservoir water washing).

That is, the method of the present invention not only enables water-saving treatment but also eliminates the need for piping for installing an automatic processor.

As a method of reducing the amount of replenishment, a multistage countercurrent system (for example, two stages, three stages, etc.) has been known for a long time. If this multistage countercurrent method is applied to the present invention, the photosensitive material after fixing will be processed in a progressively cleaner direction, that is, in sequential contact with the processing solution that is not contaminated with the fixer, resulting in even more efficient processing. Washing is done.

For the above-mentioned water-saving treatment or piping-free treatment, it is preferable to apply anti-mold means to the washing water or the stabilizing liquid.

Anti-mildew methods include the ultraviolet irradiation method described in JP-A No. 60-263939, the method using a magnetic field described in JP-A No. 60-263940, and the use of ion exchange resin described in JP-A No. 61-131632. How to make pure water, patent application 1986-
No. 253807, No. 60-295894, No. 61-6
The method using the antibacterial agent described in No. 3030 and No. 61-51396 can be used.

Furthermore, L, l! , West"Water Qual
ity Cr1teria'PhotoSci &
Eng, Vol, 9 fh6 (1965)
.

M, W, Beach lIMicrobiology
cal Growths in MotionPict
ure Processing” SMPTE Jou
rnal Vol, 85.

(1976), R,0, Deegan, Photo
ProcessingWash Water Bioc
Imaging Tech 10
.

No. 6 (1984) and JP-A-57-8542, 5
No. 7-58143, No. 58-105145, No. 57-
No. 132146, No. 58-18631, No. 57-97
Antibacterial agents, antihypertensive agents, surfactants, etc. described in No. 530 and No. 57-157244 can also be used in combination.

Additionally, R, T, Kreim
an, J, Image, Tech 10. (
6) Isothiapurine compounds described in 242 (1984), Research Disclosure (R,D) No. 2
Isothiazoline compounds described in Vol. 05, No. 20526 (May 1981), Vol. 228, No. 22
845 (April issue, 1983), compounds described in Japanese Patent Application No. 1983-51396, etc. can also be used together as antibacterial agents (formerly Crobioc, IDE).

In addition, "Chemistry of anti-bacterial and anti-mildew" by Hiroshi Horiguchi, Sankyo Publishing (Showa 5)
7), ``Handbook of Antibacterial and Antifungal Technology'' Japanese Society of Antibacterial and Antifungal Research, Hakuhodo (1988) may also be included.

When washing with a small amount of washing water in the method of the present invention, it is more preferable to provide a squeeze roller washing tank as described in Japanese Patent Application No. 172968/1983.

Furthermore, part or all of the overflow liquid from the washing or stabilizing bath, which is generated by replenishing the washing or stabilizing bath with anti-mold water according to the treatment according to the method of the present invention, is used in Japanese Patent Application Laid-Open No. 1986-1999. As described in Japanese Patent Application No. 235133, it can also be used in a processing liquid having a fixing ability, which is a processing step before that.

When the silver halide photosensitive material of the present invention is processed in an automatic processor that includes at least the steps of development, fixing, washing (or stabilization), and drying as described above, the silver halide photosensitive material of the present invention can be processed according to the conventional standard 4! ￥RP processing requires the process from development to drying to be completed within 90 seconds, and ultra-rapid processing requires completing the process from development to drying within 60 seconds.
That is, from the point at which the tip of the photosensitive material begins to be immersed in the developer, it is dried through fixing, washing (or stabilization) steps, and then
The time it takes for the tip to exit the drying zone (so-called D
It is characterized in that the dry to dry time) is within 60 seconds.

As described above, by using the photosensitive material of the present invention, extremely rapid processing unprecedented in the art can be effectively achieved without adversely affecting other performances (image quality, etc.).

In the present invention, "development time" refers to the time from when the leading edge of the photosensitive material to be processed is immersed in the developing tank liquid of an automatic processing machine until it is immersed in the next fixing solution. The "washing time" is the time from immersion to the next immersion in the washing tank solution (stabilizing solution), and the "drying time" is the time spent immersed in the washing tank solution. 1
The automatic processor is equipped with a drying zone in which hot air of 00° C., preferably 40° C. to 80° C., is blown, and the term refers to the time the product is in the drying zone.

In order to achieve the dry-to-dry rapid processing of the present invention within 60 seconds, the development temperature and time should be approximately 25°C to
6 seconds to 20 seconds at about 50°C, preferably 30°C to 40°C
More preferably, the time is 6 seconds to 15 seconds.

The fixing temperature and time are the same as for development, approximately 20°
C to about 50°C for 6 seconds to 20 seconds, preferably 30°C to 4
More preferably 6 seconds to 15 seconds at 0°C.

The water washing or stabilization bath temperature and time are preferably 6 to 20 seconds at Q'C to 50°C, more preferably 6 to 15 seconds at 15 to 40°C.

According to the method of the invention, the developed, fixed and washed (or stabilized) photographic material is dried by squeezing out the washing water, ie passing through a squeeze roller. Drying at approximately 40°C
Drying is carried out at about 100°C, and the drying time can be changed as appropriate depending on the surrounding conditions, but it is usually about 5 seconds to 30 seconds, particularly preferably about 5 seconds to 20 seconds at 40°C to 80°C. .

The maximum density (Dm>) in the present invention is from 2.7 to 4.0 degrees, but it is preferable to control the degree of emulsion scattering so that Dm falls within this range in all general-purpose processing.

A simple method is FPM-4 manufactured by Fuji Photo Film ■.
00 (automatic processor) with RD-3 (developer) and Fuji F (fixer)
Dry at a developing temperature of 35°C.

If Dm is adjusted so that Dm=2.7 to 4.0 when processing for Dry 9Q seconds, Dm in most rapid processing can be within this range.

The direct positive halodane-based photographic material of the present invention can be applied to various uses. For example, various photosensitive materials for printing such as duplication, reproduction, and offset mastering; special photosensitive materials for X-ray, flash photography, and electron beam photography; and general copying and microcopying;
It is used in various direct positive photographic photosensitive materials such as direct positive color, quick stabilized, diffusion transfer, color diffusion photography, and -bath development and fixing.

(Examples) The present invention will be explained in more detail with reference to Examples below, but the embodiments of the present invention are not limited thereto.

Example 1 1. Preparation of silver halide emulsion of the present invention In a reaction vessel heated to 55°C containing gelatin and potassium bromide, structural formula +10 CII□C1l□5C112 was added.
After adding an appropriate amount of thioether of CI12SC112CII□O11, silver nitrate aqueous solution and potassium bromide aqueous solution were added while maintaining the PAg value in the reaction vessel at 7.6. Yong? (1) was added in a controlled manner to form particles. The amount of thioether was adjusted to give an average particle size of 0.2 μ, 0.

They were 22μ, 0.30μ, 0.38μ, and 0.42μ.

These particles are cubic and monodisperse with 98% of all particles within ±40% of the average particle size. After desalting these emulsions, they were adjusted to Pl(=6.8 and PAg=8.9) and then heated to 65°C with thiourea dioxide and chloroauric acid for 40 to 100 minutes to form fog nuclei. At this time, by changing the exposure time to thiourea dioxide (the amount of chloroauric acid was set to 2°0x1 mol Ag), Fuji Photo Film was coated with the additives described later. Automatic processor FPM-4000, developer RD-3, 35°Dry
To Dry: Desired Dm of 2.7 to 4 after 90 seconds processing
．． I adjusted it so that it was 0.

Emulsion A was an emulsion with an average size of 0.20 .mu.m cube, which was heated at 65.degree. C. to which 0.15 .mu.l mol Ag of thiourea dioxide was first added, followed by 2.0 .mu.l mol Ag of chloroauric acid, and then sifted for 80 minutes.

A cubic emulsion with an average size of 0.22 microns was sifted for 80 minutes with 0.25 μl of thiourea dioxide, 1 mole of Ag, 2 of chloroauric acid, and 1 mole of Ag.

Emulsion C is a cubic emulsion with an average grain size of 0.30μ, 0.25μ1 mol Ag of thiourea dioxide, and 2.0μ1 chloroauric acid.
It was sifted with Mole Ag for 60 minutes.

Emulsion d is a cubic emulsion with an average grain size of 0.38μ, 0.15mg of thiourea dioxide, 1 mol of Ag, and 2.0μ of chloroauric acid.
It was sifted with 1M Ag for 50 minutes.

Emulsion e is a cubic emulsion with an average grain size of 0.42μ, 0.20mg of thiourea dioxide, 1 mol of Ag, and 2.0μ of chloroauric acid.
It was sifted with 1M Ag for 50 minutes.

2. Preparation of emulsion coating solution Put 1000 g of each of emulsions a, b, c, d, and e into a container.
After heating and dissolving at 40°C, the sensitizer 5-ethoxycarbonyl-1,3,3°trimethyl-2-(2-(
2,4-dimethyl-9oxopyrazolo(5,1-b)quinazolin-3yl)vinylcou 3H-indolium 4-
0.8% methanol of methylhenzenesulfonate? Yong? & 50 cc, wetting agent trimethylolpropane 50
% aqueous solution 20cc, stabilizer 4-hydroxy-6-methyl-1,3,3a,7-titrazaindene aqueous solution, coating aid dodecylbenzenesulfonate aqueous solution, binder aid polyacrylamide aqueous solution, thickener polypotassium p-vinylbenzene A sulfonate compound aqueous solution was added to prepare each coating solution.

A and B are coating solutions from emulsions a, b, c, d, and e.

Name them C, D, and E, respectively.

3. Preparation of coating solution for the surface protective layer of the photosensitive material layer Add a thickening agent to a 1Qwt% gelatin aqueous solution heated to 40°C, a thickener, a sodium polystyrene sulfonate aqueous solution, Mann 1~ agent, and two sizes of gelatin. Polymethyl methacrylate a particles (average particle size 3μm and 0°8μm) hard 1111N, N'-ethylenebis(vinylsulfonylacetamide), coating aid sodium t-octylphenoxyethoxyethanesulfonate aqueous solution, and antistatic agent with the following structure. A coating solution was prepared by adding an aqueous polyethylene surfactant solution, an aqueous solution of a fluorine-containing compound having the structure shown below, an aqueous polyacrylamide solution, polyacrylic acid, and silica. The hardening agent is
1.5 wt% of the total amount of gelatin in the protective layer and emulsion,
The test was repeated 8 times so that the water swelling at 20° C. was 150%.

CBf, 7SO2N-C,H.

(Cll zctlo)r) Cll 2)7 So J
aC+611:++0(CHzCIIO)TollCe
F+7SOJ 4, preparation of bank coating solution l Qwt% gelatin water solution heated to 40”C!1
000 g, thickener polyethylene sodium sulfonate aqueous solution, 400 cc each of the following 6% aqueous dye solutions, hardener N, N'-ethylene bis-(vinylsulfonylacetamide) aqueous solution, coating aid t-octylphenoxyethoxyethane sulfate. Sodium fluorinate aqueous solution, polymethyl methacrylate fine particles (average particle size 1.2 μm)
, silica, and an aqueous solution of a copolymer of methyl methacrylate and ethyl acrylate were added to prepare a coating solution.

Dye 5O3K 03K SO, 5. Preparation of coating solution for surface protection layer of hack layer Add 1 Qwt% gelatin aqueous solution heated to 40°C, thickener polystyrene sodium sulfonate aqueous solution, cloak agent polymethyl methacrylate fine particles (average particle size 3.0 μm),
An aqueous solution of sodium t-octylphenoxyethoxyethanesulfonate as a coating aid and a polyethylene surfactant Cl611330 (C1) with the following structure as an antistatic agent.
l□CIh0>111CaF I? 5O2N (C3
H7) -(C112CH20)T(C112)ts
OJaC8F,,SO□N(C311t)CII□C0
0 and CaF I 73O□N (C3tlt) (C)12
A coating solution was prepared by adding an aqueous solution of cII□0h11 and an aqueous solution of a fluorine-containing compound having the following structure.

6. Preparation of coating sample The above-mentioned Huck coating solution was applied to one side of the polyethylene terephthalate support together with the Huck surface protective layer coating solution, with a gelatin coating amount of 0.7 g/m' for the Huck layer and 2.5 g/m' for the bank protective layer. It was applied so that the total amount of m2 was 3.2 g/M.

Subsequently, on the opposite side of the support, the emulsion coating solution described in 2 and the protective layer coating solution described in 3 were applied in this order starting from the support side. The amount of gelatin applied for the protective layer is 1.4g.
/rrF is set as common. Coating samples were prepared by changing the coating amount of the emulsion coating solution as follows.

Emulsion coating solution A with a coated silver amount of 2.6 g/m was used as coating sample (2).

Emulsion coating solution B with a coated silver amount of 2.6 g/rrf was used as a sample [phase].

Sample O was prepared using emulsion coating solution C in which the amount of silver coated was 2.0 g/m.

A sample (2) was obtained by using emulsion coating solution C to reduce the coating silver amount to 2.2 g/%.

A sample (2) was prepared using emulsion coating solution C with a coated silver amount of 2.6 g/bo.

The amount of silver coated with emulsion coating solution C was 3.3 g/n? This was designated as sample ○.

Samples were bound using emulsion coating solution C with a coated silver amount of 3.5 g/bore.

An emulsion coating liquid with a coated silver amount of 2.6 g/bore was used as sample (2).

Sample (2) was prepared using emulsion coating solution E with a coated silver amount of 2.6 g/pot.

7. After the various coated samples of development process 6 were kept at a temperature and humidity of 20° C. and 165% RH for 7 days, B1. Sensitometric exposure for 5 seconds was performed with a B light source.

After exposure, conventional RP 90 second processing was performed at 35° C. using an automatic processor FPM-4000 manufactured by Fuji Photo Film ■, developer RD3, and fixer Fuji F.

In addition, Fuji Photo Film offers ultra-quick processing without dura mater.
DrytoDr CR-i-1-414 automatic processor
It was carried out at y50 seconds using developer RD-10 and fixer RP10.

8. Evaluation of photographic properties Based on the Sensi I-metry described in 7, it was determined that the highest density Dm was 2.7 or more, which is practically essential, and 4.0 or less, which is almost sufficient, as suitable.

9. Evaluation of film detection stability Pass 20 sheets of the sample described in 6 cut into four pieces through the automatic processing machine FPM-4000, and calculate the number of times the processing liquid automatic replenishment mechanism of the automatic processing machine does not operate normally. It was measured.

Those that worked normally on all 20 sheets were considered acceptable, and those that showed even one abnormality were rejected.

10. Evaluation of film silver image color tone after processing An original chest photograph was exposed to the sample described in 6 using a DuPont Duplicator with a BLB light source. The exposure time was changed depending on the sample so that the density of the finished replicated image was appropriate. Processing is RD with FPM-4000
-335°Fuji F standard RP 90 seconds.

The finished duplicate film was placed on a Scherkasten for medical image interpretation and the silver image color tone was evaluated. Skilled in interpreting images 5
I asked someone to point out where the visual contrast was reduced because the silver image turned into yellow steel.

Those in which the visual contrast was 1 to 1 or more decreased by 2 Å or more were judged as not acceptable. Those that did not meet this criteria were judged to be appropriate.

11. Results The results are shown in Table 1.

It can be seen that the combination of the present invention is good in terms of Dm = 2.7 to 4°0, film detection stability in an automatic processor, and silver image color tone of the film after processing is not yellowish.

Example 2 10 Preparation of silver halide emulsion of the present invention In a reaction vessel heated to 55°C containing gelatin and potassium bromide, the structural formula 110CII2CIl□5CII□C was added.
Appropriate amount of thioether of H,5CII□C11□01 (and sodium Hensensulfinate (Log 1 mol Ag
> was added, the pH was set to 3, and p, Ag in the reaction vessel
While keeping the value at 7.6, a potassium bromide aqueous solution to which hexachloroiridate (Ill) was added so that the molar ratio of iridium to silver was 10-6 mol was subjected to a controlled double jet method. First, a core was made with half of the total amount of silver. A potassium bromide aqueous solution containing the remaining half of the total silver amount was added to the reaction vessel containing the core by a controlled double jet method to form a shell. Adjust the amount of thioether to bring the average particle size to 0.
19μm, 0゜21μm, 0.30μm, 0.40μm
, 0.43 μm.

These particles were cubic and monodisperse with 98% of all particles within ±40% of the average particle size. After desalting these emulsions, the pH was adjusted to 6.8 and the pAg to 8.9, and then thiourea dioxide was heated to 65°C with chloroauric acid to form fog nuclei over 40 to 100 minutes. . Thiourea dioxide 0. 2■ 1 mol Ag, chloroauric acid 2ml
1 mol Ag, fogging time is 50' and 60', respectively.
', 65' and 60' to achieve the maximum sensitivity. The emulsion names are high-sensitivity emulsions h-1 and h2, respectively, based on the size.
, h-3, h-4, and h-5.

Next, an appropriate amount of the above-mentioned 1,000-onythyl was added to a container heated to 55°C containing gelatin, potassium bromide, and water, and then an aqueous solution of silver nitrate was added while maintaining the I) Ag in the reaction container at 7.6. Particles were formed by adding an aqueous solution of potassium chloride using a controlled double jet method. Adjust the amount of thioether to adjust the average particle size to 0.19μm, 0.21μm.
Four types were made: m10°30 μm, 0.40 μm, and 0.43 μm. After desalting, the pH was adjusted to 6.8 and I) Ag to 8.9, and then fogging was carried out at 65°C for 60' with 1 mol Ag of thiourea dioxide and 2 1 mol Ag of chloroauric acid, respectively. , 65', 70' and 60'.
Approximately 1°Oj each! Sensitivity was set to ogE low sensitivity. These emulsions are medium-sensitivity emulsions m-1, m-2, and m-3.
, m-4, and m-5.

Next, the average particle sizes without iridium mentioned above were 0.19 μm, 0.21 μm, 0.30 μm, and 0.40 μm.
μm, 0.43 μm, the inflating conditions were 1.2 x 1 mol Ag of thiourea dioxide and 2 x 1 mol Ag of chloroauric acid.
The fogging time was 70', 80', and 90' at 5℃, respectively.
, 85', and the sensitivity was set to about 1.0 ρogE lower than the medium speed emulsion. These emulsions were converted into low-sensitivity emulsions β-1,1
2, j2-3, N-4, and N-5.

Next, the average particle size of the aforementioned iridium-free particles was 0.19 μm, 0.21 μm, and 0.3amO240 μm.
, 0.43 μm, the fogging conditions were 9 1 mol Ag of thiourea dioxide and 4 1 mol Ag chloroauric acid.
The fogging time was 70', 70', and 90' at 5°C, respectively.
Approximately Q, 8ffog compared to low-speed emulsion with a period of >70'
E Sensitivity was set to low sensitivity. These emulsions were named extremely low sensitivity emulsions n1, n-2, n-3, n-4, and n-5.

2. Preparation of emulsion coating solution Low sensitivity emulsion n-1, p-2, β=3,! -4,ll-5
and ultra-low sensitivity emulsions n-1, n-2, n-3, n-4, n-
Weigh out 500g of each of 5, mix, and heat the container to 40°C.
After heating and dissolving the sensitizer 5-ethoxycarbonyl-1,3
,3-trimethyl-2C2-(2,4-dimethyl-9-
Oxopyrazuro(5,1-b)quinazolin-3-yl)
Vinyl]3H-indolium 4-methylhenzenesulfonate 0.8% methanol solution 53cc, compound (1
-2) 0.5% methanol solution 17cc, wetting agent 1-
Rime 1,000 roll propane 50% aqueous solution 20CC1 stabilizer 4
-Hydroxy-6~methyl-1,3゜3a,7-chitrazaindene aqueous solution, coating aid dodecylhenzenesulfonate aqueous solution, binder aid polyacrylamide aqueous solution, thickener polybotacium p-vinylbenzenesulfone (- An aqueous compound solution was added to obtain a low-sensitivity emulsion coating solution.

That is, 1-1/n-1, N-2 of the weighed mixed emulsion
/n-2, II-3/ n-3,1,-4/ n-4
, p5/n-5 to L-1, L-2,
They were named L3, ■, -4, and L-5, respectively.

Compound (1-2) for high-speed emulsions h-1, h-2, h-3, h-4, h-5 and medium-speed emulsions m-1, m-2, m-3, m4, m-5 0. The same additions as above were made except that the addition of the 5% methanol solution was omitted to obtain a high-sensitivity side coating solution. Zunawachi weighed mixed emulsion h-1/m-1,
h-2/m2, h-3/m-3, h-4/m-4, k
+ Coating liquid from -57m-5 H-1, H-2, ■]
They were named -3, H-4, and H-5, respectively.

3. Preparation of coating solution for surface protective layer of sensitive material layer (3) of Example 1
).

4. Preparation of bank coating solution It was the same as that described in (4) of Example 1.

Preparation of coating solution for surface protective layer of 568 layers Example 1 (
It is the same as that described in 5).

6. Preparation of coating sample The above-mentioned Huck coating solution was applied to one side of the polyethylene terephthalate support along with the Huck surface protective layer coating solution, with a gelatin coating amount of 0.7 g/m' for the bank layer and 2 for the Huck protective layer.
．． It was coated at 5 g/m, for a total of 3.2 g/m'.

Subsequently, on the opposite side of the support, place the low-sensitivity side coating liquid L-n, the high-sensitivity side coating liquid Hn, and the surface protective layer coating liquid of the emulsion coating liquid described in 2 in this order from the support side. Coated. The coating amount of gelatin in the protective layer was kept constant at 1.4 g/n. Desired coating samples were prepared as follows by varying the coating amounts of emulsion coating solutions Ln and H-n.

The coating silver amount of each of emulsion coating solution 7-1 and H-1 was 1
．． 2sg/=sample of the applied material with a total binding weight of 2.5g/m■
And so.

The coating silver amount of each of emulsion coating solutions L-2 and H-2 was set to 1.
A coated product with 25 g/% binding and a total of 2.5 g/A was used as sample (2).

The coating silver amount of each of emulsion coating solutions L-3 and H-3 was set to 0.
The coating material was 95 g/m, and a total of 19 g/m was used as sample (2).

The coating silver amount of each of emulsion coating solutions L-3 and H-3 was set to 1.
Sample (2) was a coated material with a total weight of 2.1 g/m.

The coating silver amount of each of emulsion coating solutions L-3 and H-3 was set to 1.
65 g/m, and a coated material with a total weight of 3.3 g/m was designated as sample (2).

The coating silver amount of each of emulsion coating solutions L-3 and H-3 was set to 1.
88/m, and a total of 3.6g7'rd of applied material was sampled.
And so.

The coating silver amount of each of emulsion coating solutions L-4 and H-4 was set to 1.
25g/n (stitched, a total of 2.5g/m of coated material is sampled)
And so.

The coating silver amount of each of emulsion coating solutions L-5 and H-5 was 1
．． 25 g/m, and a coated material with a total weight of 2.5 g/rd was designated as sample (2).

The coated emulsion grains of coated samples (1) to (2) are all substantially monodisperse.

7. Development Process After keeping the various coated samples in 6 for 7 days at a temperature and humidity of 20°C and 65% RH, they were subjected to 5-second sensitometry at room temperature using a DuPont Duplicator with a BLB light source. exposure was performed. After exposure, three types of development processing were carried out using an automatic processing machine using the following processing solutions and processing steps.

) Conventional RP 90 second processing developer RD-3. Fixer: Fushi F Temperature: 35° Automatic processor: FPM-4000 (manufactured by Fuji Photo Film) ii) Ultra-quick 47-second processing developer containing a hardener in the developer: XD-3R, Fixer: XF -3R35° automatic developer, 5RX-501 (manufactured by Konica) 111) Ultra-quick 50-second processing developer that does not contain a hardening agent, R1)-10, fixer; RF-1035° automatic developer Machine: CR-LP-414 automatic processor part that can process for 50 seconds.

(Manufactured by Fuji Photo Film ■) 8. Evaluation of processing suitability From the sensitometry results obtained by the method described in 7, the maximum density Dm is 2.7 or more, which is practically necessary, and is not practically necessary, and the average It was determined that 2°7≦Dm≦4.0 was appropriate, except for Dm=4 or more where the floor i1!1.0±0°2 could hardly be obtained. Others were rejected.

9. Evaluation of film detection stability Pass 20 sheets of the sample described in 6 cut into four pieces through the automatic processor FRM-4000, and calculate the number of times the automatic processor's processing liquid replenishment mechanism does not operate properly. It was measured.

Those that worked normally on all 20 sheets were considered acceptable, and those that showed even one abnormality were rejected.

10. Evaluation of film silver image color tone after processing The original chest photograph was exposed to the sample described in 6 using a BLB light source in a Deco-Bon duplicator.

The exposure time was changed depending on the sample so that the density of the finished replicated image was appropriate. Processing is done using PRM-4000.
The standard RP of 335° Fuji F was 90 seconds.

The finished duplicate film was placed on a medical image reading scanner to evaluate the silver image color tone. We asked five people who are experts in image interpretation to point out when a silver image becomes yellowish, resulting in a decrease in visual contrast and luster.

Those in which visual contrast i/deterioration of 2 Å or more was indicated were judged as negative. Those that did not meet this criteria were judged to be appropriate.

11. Results The results are shown in Table 2.

The treatment suitability of the combination of the present invention is that of conventional RP.
This applies to all 90-second processing, ultra-quick 47-second processing using a developer containing a hardening agent, and ultra-quick 50-second processing using a developer containing no hardening agent. Furthermore, it can be seen that both the film detection stability in the automatic processing machine and the silver image color tone of the processed film do not have a yellowish tinge are good.

Claims (1)

[Claims] The average grain size of the silver halide emulsion is 0.21 to 0.4
A pre-fogged type autopositive sensitive material with a thickness of 0 μm and a coated silver amount of 2.1 to 3.4 g/m^2 is exposed and developed to form an image with a maximum density (Dm) of 2.7 to 4.0. how to.