JPH03152529A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the silver halide photographic sensitive material which is improved in the degree of the black color of image silver and has a high sensitivity and high covering power by incorporating a nondiffusive compd. which loses the capacity to release a diffusive dye when oxidized into a photosensitive material layer. CONSTITUTION:The nondiffusive compd. Which loses the capacity to release the diffusive dye when oxidized is incorporated into a silver halide emulsion layer and/or other layers in such a manner that the dye images corresponding to silver development are formed. The respective image densities formed by the nondiffusive compd. are preferably <=1/10 the corresponding silver image density. The photographic sensitive material having the improved degree of the black color of the image silver and the high sensitivity and high covering power is obtd. in this way.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a silver halide photographic light-sensitive material (hereinafter referred to as "photographic window light-sensitive material"), and in particular, it relates to a silver halide photographic light-sensitive material (hereinafter referred to as "photographic window light-sensitive material"), and in particular, a silver halide photographic light-sensitive material (hereinafter referred to as "photographic window light-sensitive material"). This invention relates to photographic materials with high sensitivity and high covering power.

(Prior Art) The covering power of silver halide emulsions is of great interest to emulsion manufacturers. The reason for this is that by using a high covering power emulsion, the amount of silver required to maintain a constant optical density can be saved. In order to increase the covering power of silver halide emulsions, US Pat. ,9
No. 96.322, No. 3.178.282, No. 3,
No. 397.987, No. 3.607. No. 2'78, British Patent No. 1,426,277, etc. Furthermore, U.S. Pat.
, No. 411.986, No. 4,434,226, No. 4,413.053, etc. Furthermore, JP-A No. 58108.526 discloses that extremely high photosensitivity and covering power can be obtained by so-called epitaxial tabular grains in which another silver salt is placed at a specific location on a tabular grain having a high aspect ratio and a small grain thickness. This is disclosed. In addition to the above-mentioned emulsions, high-sensitivity fine-grain emulsions with small average grain sizes and high-sensitivity tabular grain emulsions with small average grain thicknesses have higher silver covering power than emulsions with larger average grain sizes and average grain thicknesses. Yes (known)

(Problems to be Solved by the Present Invention) However, the color tone of the developed silver of the emulsion grains that provide the above-mentioned high silver covering power almost always depends on the grain size and grain thickness, but images are observed to have a yellowish or greenish tinge. give an unpleasant impression to the person. The reason for this yellowish or greenish tinge is that as the particle size and thickness decrease, the size and thickness of the developed silver also decreases, and the scattering of blue light components increases, resulting in light with a strong yellowish tinge. This phenomenon occurs when silver halide emulsions are fine grain emulsions (for example, average grain size 0.4μ or less) and tabular grains with thin grains (for example, grain thickness 0.4μ or less).
This is especially a problem when using the following). Furthermore, it is known that even with potato-shaped halogenated particles, which are generally said to have good color tone, the color tone changes toward green when the hardness of the sensitive material is lowered to form a soft film. In general, a so-called toning agent is often used to adjust the color tone of developed silver and obtain a cool black tone. For example, certain mercapto compounds are used for that purpose. However, even if such a conventionally well-known color toning agent is applied to an emulsion consisting of highly sensitive silver halide grains, it causes a significant desensitization effect and cannot be put to practical use. Furthermore, Japanese Patent Application No. 1276/1983 discloses a technology for improving the color tone of silver images by incorporating a fluorescent brightener into a light-sensitive material consisting of a tabular silver halide grain emulsion whose grain size is at least five times the grain thickness. Disclosed. As stated in the patent, this technique is very effective for observation under a reflected light source, but is almost ineffective for observation under transmitted light.

(Problems to be Solved) The purpose of the present invention is to eliminate the drawbacks of the above-mentioned techniques, and to provide a silver halide photosensitive material having high sensitivity and high covering power, with a cool black tone and improved blackness of the image silver. It is to provide.

Conventionally, a method for solving this problem has been to change the color tone of the support itself depending on the type of film, but this increases costs in terms of productivity management.

Also known is a method of incorporating a diffusion-resistant dye that is stable during and after processing into the emulsion layer and/or other layers, as disclosed in JP-A-62-276539. However, the method disclosed in the above-mentioned patent has the disadvantage that the unexposed area also contains the same amount of dye, which increases the fog density.

(Means for Solving the Problems) As a result of extensive research, the present inventors have found that by incorporating a non-diffusible compound that loses the ability to release diffusive dyes when oxidized into the light-sensitive material layer. To obtain a silver halide photographic light-sensitive material with high sensitivity and high covering power, which has low fog density and has improved blackness of image silver that gives a cool black tone over a wide density range from low density areas to high density areas. I was able to do that.

Dye images compatible with silver development are formed by non-diffusible compounds that lose their ability to release diffusible dyes upon oxidation.

Examples of such compounds include U.S. Pat. No. 4,199.
No. 354, No. 3.980,479, JP-A-62-24
As disclosed in German Patent No. 5263 and German Patent No. 2,654°213, a diffusible dye is released by intramolecular nucleophilic reaction or intramolecular electron transfer in the presence of an alkali in a reduced state; Examples include compounds that reduce the rate of release of the diffusible dye.

Examples of the diffusible dye to be released include those having a predetermined maximum wavelength from among anthraquinone dyes, azo dyes, azomethine dyes, indoaniline dyes, oxonol dyes, carbocyanine dyes, styryl dyes, triphenylmethane dyes, etc. selected. In consideration of stability to development processing, light fastness, desensitization, capri stain, and other effects on photographic performance, anthraquinone dyes, azo dyes, azomethine dyes, and indoaniline dyes are preferably used.

Compound example (1) Ns +1sc2 CzHaSOJa (10) (11) N.H.

(12) (15) (18) (16) (17) NiYU1L115LINIH (20) The density of the blue dye image formed corresponding to the silver image by these compounds in the present invention is the silver image density. 1710 of
Below, it is especially preferable that it is 1720 or less. The minimum concentration is preferably 0.01 or more.

The concentration in the present invention is measured using a Macbethfi meter TR-9.
Measured by Type 27 (Visual Density).

When the blue dye image density exceeds 1/10 of the silver image density, the color tone becomes too blue, which is undesirable.

The coating amount of the compound of the present invention is 5 .mu.-300 .mu./nf, preferably 15 .mu.-200 .mu./nf.

The coating amount of silver halide at this time is 1.5 to 7 g/rrf
, preferably 2 to 5 g/bo.

Furthermore, the amount of binder applied to form the film is 1°5 to 7g.
/rrf, preferably 2 to 5 g/rd.

By minimizing the amount of silver halide and binder applied in this way, rapid processing can be achieved.

The compounds of the present invention can be added alone or in combination. When combined, a compound having a maximum absorption wavelength between 510 and 570 rv and 570 to 700 n-
It is desirable to combine the compound with a compound having a maximum absorption wavelength between

As another method for introducing the compound of the present invention into the hydrophilic colloid constituting the photographic layer, a known method of emulsifying a color coupler and adding it to the hydrophilic colloid layer can be used. i.e., U.S. Patent No. 2,322
A dispersion of the present compound in an organic solvent can be added to a photographic hydrophilic colloid by methods such as those described in US Pat. Organic solvents for this purpose have a boiling point of about 175
It is made of a high boiling point organic solvent with a boiling point of 30° C. or more or a low boiling point N solvent with a boiling point of 30° C. to about 150° C., either alone or in a mixture of both in an arbitrary ratio. As the above-mentioned low boiling point organic solvent, among alcohols, ethers, glycols, ketones, esters, and amides, those that do not affect the photographic properties of form vI can be used. In addition, as the above-mentioned high boiling point organic solvent, di-n-
Butyl phthalate, hensyl phthalate, triphenyl phosphate, tri-cresyl phosphate, diphenyl mono-P tert-butylphenyl phosphate, monophenyl di-p-tert-butylphenyl phosphate, 2,4-di-monoamylphenol, N
, N-diethylrauramide, trihexyl phosphate, and the like can be used.

The step of introducing the compound of the present invention into the hydrophilic colloid constituting the photographic light-sensitive material may be carried out at any step in the production of the photographic light-sensitive material, but it may be carried out in any step before the coating step, especially when the photographic coating liquid is introduced into the hydrophilic colloid constituting the photographic light-sensitive material. Preferably, the process of preparing

When the compound of the present invention is soluble in an organic solvent, it can be dissolved in a low boiling point organic solvent or an organic solvent miscible with water and added to the hydrophilic colloid layer. If the compound is water-insoluble, the compound of the present invention can be solid-dispersed by a solid-dispersion method as described in EP276566A1 and added to the hydrophilic colloid layer.

Typical examples of emulsions having high covering power used in the present invention include tabular emulsions and fine grain emulsions.

The method of the present invention is particularly suitable for silver halide photographic emulsions of 0.4μ
In the case of tabular silver halide grains having a grain thickness of 0.5 μm or less, a fine grain silver halide emulsion of 0.5 μm or less or a mixed emulsion of a high iodine surface-sensitive emulsion and an emulsion consisting of grains whose interior is covered with fine grains is used. In the case of the photosensitive material used or the photosensitive material used in combination, it has a great effect of improving the color tone by making it a neutral color.

Another effective method is to incorporate the compound of the present invention and a tone-adjusting dye according to the method described in JP-A No. 62-276539 to improve the degree of blackness over the range from low density to high density. For example, a silver halide photographic light-sensitive material in which a dye having a maximum absorption wavelength of 570 to 700 nm according to JP-A No. 62-276539 and a magenta coloring dye corresponding to the silver development according to the present invention is present, or JP-A No. 62-276
A silver halide photographic material containing a dye having a maximum absorption wavelength between 520 and 560 nm according to No. 539 and a cyan color-forming dye corresponding to the silver development of the present invention can be considered.

Next, the silver halide grains used in the present invention include silver chloride,
Any silver halide consisting of chlorine, bromine, iodobromide, such as silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide, silver chloroiodobromide, etc. may be used, but in particular, silver bromide, Silver iodobromide, silver chloride,
Silver chlorobromide and silver chloroiodobromide are preferred. Silver iodide in the silver halide is preferably 0 to 20 mol%, particularly preferably 0 to 10%.

The grains may be so-called regular grains having regular crystal bodies such as cubes, octahedrons, and tetradecahedrons, and may also be potato-shaped, spherical, plate-shaped, or tabular with a particle diameter of 5 times or more the particle thickness. It may be one having an irregular crystal form or a complex thereof.

The grain size of the silver halide may be a monodisperse emulsion with a narrow distribution, or a polydisperse emulsion with a wide distribution.

The light-sensitive material used in the present invention does not have to have only one silver halide emulsion layer, but may have two or more layers, and two or more types of emulsions with different grain sizes, sensitivities, etc. may be mixed or used in separate layers. Good too. Further, the emulsion layer is not limited to one side of the support, but may be provided on both sides.

These light-sensitive emulsions may be mixed with substantially non-light-sensitive emulsions (for example, internally covered fine grain emulsions), or may be used by coating them in separate layers.

Furthermore, even if the crystal structure of silver halide grains is similar up to the inside, there are also grains with a layered structure in which the inside and outside are different, British Patent No. 635,841, US Patent No.
It may also be of a so-called conversion type as described in No. 22.318. Further, either a type in which a latent image is mainly formed on the surface or an internal latent image type in which a latent image is formed inside the particle may be used.

The emulsion of the present invention can contain heavy metal ions such as iridium ions. In order to contain iridium ions, a water-soluble iridium compound (for example, hexachloroiridate (III) salt, hexachloroiridate (IV) salt) is added to water i8? This is achieved by adding in the form of &.

It may be added in the same aqueous solution form as silver 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 chemical sensitization.
Particularly preferred is addition during particle formation.

During the formation of silver halide grains, for example, ammonia, rhodanpotash, rhodanammonium, thioether compounds, thione compounds, amine compounds, etc. can be used as silver halide solvents to control grain growth.

In addition to silver halide solvents, compounds that adsorb to the grain surface to control crystal habit, such as cyanine sensitizing dyes, tetrazaindene compounds, and mercapto compounds, can be used during grain formation.

Next, the tabular grains used in the present invention will be explained.

As the tabular grains having an average grain thickness of 0.4 μm or less in the present invention, grains having a grain size of three times or more the grain thickness are preferably used from the viewpoints of sensitivity, granularity, sharpness, etc.

More preferably 4 to 100 times, more preferably 5 to 50 times
times, particularly preferably 5 to 20 times.

Further, the proportion of tabular silver halide grains in the projected area of all silver halide grains is 50% or more, preferably 70% or more, particularly preferably 85% or more. By using such an emulsion, a silver halide photographic emulsion having high spectral sensitivity and excellent suitability for high illuminance can be obtained.

Further, the diameter of the tabular silver halide grains is 0.5 to
It is 10μ, preferably 0.6 to 5.0μ, particularly preferably 1 to 4μ. Here, the tabular silver halide grain diameter refers to the diameter of a circle having an area equal to the projected area of the grain.

In the present invention, more preferred tabular silver halide grains have a grain diameter of 0.6 μm or more and 5.0 μm or less, a grain thickness of 0.2 μm or less, and an average diameter/average thickness of 5 or more. 50 or less.

More preferably, the particle diameter is 1.0 μm or more and 5.0 μm.
The following is a case of a silver halide photographic emulsion in which grains having a diameter/thickness of 8 or more occupy 85% or more of the total projected area of all silver halide grains.

The tabular silver halide grains may be any of silver chloride, silver bromide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide;
Silver iodobromide containing 20 mol% or less of silver iodide or silver chloride 50 mol% or less, silver chloroiodobromide and silver iodobromide containing 10 mol% or less of silver iodide are more preferable, and the composition in mixed silver halide The distribution may be uniform or localized, but uniform distribution is preferable.

Further, the particle size distribution may be narrow or wide.

The tabular silver halide emulsion is manufactured by Cugnac.
, reports by Chatean and Dufin (D
uffin), °“Photographic Emulsion
Chemistry (Photographic emul)
sion chemistry)”, Focal Press (New York),
1966, p. 66-72, and A.P., 11. Trivelli, W.F., Smith
ith), Photographic Journal (Phot,
J.), 80.285 (1940);
It can be easily prepared by referring to the methods described in No. 13,927 and JP-A-58-113,928.

The size of the tabular silver halide grains can be adjusted by controlling the temperature, selection of the type and amount of solvent, the silver salt used during grain growth, the addition rate of halide, etc.

When producing the tabular silver halide grains of the present invention, grain size and shape (diameter/thickness ratio, etc.), grain size distribution, and grain growth rate can be controlled by using a silver halide solvent as necessary. . The amount of solvent used is 10% to 1% by weight of the reaction solution, especially 10% to 10% by weight of the reaction solution.
1% by weight is preferred.

For example, as the amount of solvent used increases, the particle size distribution can be made monodisperse and the growth rate can be accelerated.

On the other hand, there is also a tendency for particle thickness to increase with the amount of solvent used.

Often used silver halide solvents include ammonia, thioethers and thioureas.

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present.

The silver halide grains, fine silver halide grains, and highly iodine-sensitive tabular silver halide grains of the present invention can be chemically sensitized if necessary.

For chemical sensitization, for example, H Freezer (H
, Fr1eser) ed.
Die Grundlagend
er Photography Proze
sse sit Silberhalogeniden
) J (Academyshi!-'Fairrags Ak
ade+5ische Verlagegesells
chaft, 1968), pages 675-734, can be used.

Namely, sulfur sensitization using sulfur-containing compounds that can react with active gelatin and silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines); reducing substances (e.g., stannous salts, reduction aggravation method using noble metal compounds (e.g., total complex salts,
A noble metal sensitization method using Pt (complex salts of metals of group (I) of the periodic table such as Pd) can be used alone or in combination.

Various hydrophilic colloids can be used as binders in the photographic material of the present invention.

Colloids used for this purpose include, for example, gelatin, colloidal albumin, polysancharides, cellulose derivatives, synthetic resins, polyvinyl compounds including polyvinyl alcohol derivatives, dextrans, acrylamide polymers, etc. Mention may be made of hydrophilic colloids. Among these, it is preferable to use dextran and polyacrylamide in combination with gelatin, and to contain hydrophobic colloids together with hydrophilic colloids, such as dispersed polymeric vinyl compounds, especially those that increase the dimensional stability of the photographic material. Can be done. Suitable compounds of this type include water-insoluble polymers made by polymerizing vinylic monomers such as alkyl acrylate methacrylates, acrylic acid, sulfoalkyl acrylates or sulfoalkyl methacrylates.

Various compounds can be added to the above-mentioned photographic emulsion in order to prevent a decrease in sensitivity and the occurrence of capri during the manufacturing process, storage or processing of the light-sensitive material. These compounds are 4-hydroxy-6-methyl-1.

3, 3a,? A large number of compounds have been known for a long time, including -tetrazaindene, 3-methylbenzothiazole, and 1-phenyl-5-mercaptotetrazole, as well as many heterocyclic compounds, mercury-containing compounds, mercapto compounds, and metal salts.

An example of a compound that can be used is C. E. in Mies (Me)
es), T. H. Co-edited by James (Ja+nes) [
The Theory of the Photographic Process
"Raphic Process) 3rd Edition" published by The Mac+willan Company (published in 1967), Research Disclosure + -
(Research Disclosure) No. 17
Volume 6, 17643, pages 24-25, paragraph (1978)
(December 2013), citing the original documents.

The protective layer of the silver halide photographic light-sensitive material of the present invention is a layer consisting of a hydrophilic colloid, and the hydrophilic colloids used are those mentioned above.

Further, the protective layer may be a single layer or a multilayer. Preferably, a capping agent and/or a smoothing agent may be added to the emulsion layer or the protective layer of the silver halide photographic material of the present invention.

In the present invention, as a matting agent, US Pat. No. 2.992.
No. 101, No. 2,701,245, No. 4.142.8
A homopolymer of polymethyl methacrylate or a copolymer of methyl meccrylate and meccrylic acid as described in No. 94 and No. 4,396,706, starch, silica, titanium dioxide, 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, silicone compounds described in U.S. Pat. No. 3,489,576, U.S. Pat.
As examples of colloidal silica described in the publication, paraffin wax, higher fatty acid esters, starch derivatives, etc. can be used.

The silver halide photographic light-sensitive material of the present invention may further include an antihalation layer, an intermediate layer, a filter layer,
etc. can be provided.

In the photographic material of the present invention, the photographic silver halide emulsion layer and other hydrophilic colloid layers can be hardened with any suitable hardener. The dura mater level is JP-A-58-1119.
100% to 300% by measurement method according to No. 33
is desirable. These hardeners are disclosed in Japanese Patent Application Laid-Open No. 51-7602.
Vinyl sulfonyl compounds such as those described in No. 5, No. 5376026 and No. 53-77619; Hardeners having active halogens Nidioxane derivatives; Oxypolysaccharides such as nioxy starch; and the like.

The photosensitive materials of the present invention include Japanese Patent Application No. 141111/1982, 62144/1983, 27895/1995, and W.
It is also useful to have a dye-containing layer present for cross-over light blocking purposes in the manner described in O,/s 8104794, EP276566 Al.

Other additives may be added to the photographic silver halide emulsion layer, particularly those useful in photographic emulsions, such as lubricants, sensitizers, plasticizers, and the like.

The photosensitive material of the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a Zilter dye or for various purposes such as preventing irradiation or halation. dye,
Included are hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and ab dyes. Among them, oxonol dyes: hemioxonol dyes and merocyanine dyes are useful.

In the photographic material of the present invention, when dyes, ultraviolet absorbers, etc. are included in the hydrophilic colloid layer, they may be mordanted with a cationic polymer or the like.

The photosensitive material of the present invention may also contain a surfactant for other purposes. Depending on the purpose, any of nonionic, ionic, and amphoteric surfactants can be used, such as polyoxyalkylene derivatives, amphoteric amino acids (including sulfobetaines), and the like.

As antistatic agents, in particular, fluorine-containing surfactants described in U.S. Pat.
No. 2, No. 60-80848, No. 60-80846,
No. 60-80839, No. 5B-208743, No. 6
Nonionic surfactant having alkylene oxide group described in JP 0-76741 and JP-A-57-204
Polyacrylic acid described in Japanese Patent No. 540 can be preferably used. In addition, as the inorganic antistatic agent, preferably used are alkali metal nitrates, conductive tin oxide and zinc oxide described in JP-A-57-118242, or composite oxides obtained by doping these metal oxides with antimony or the like. be able to.

In the light-sensitive material of the present invention, the photographic emulsion may be spectrally sensitized to relatively long wavelength blue light, green light, red light, or infrared light using a sensitizing dye. As sensitizing dyes, cyanine dyes, merocyanine dyes, complex cyanine dyes,
Complex merocyanine dyes, holopolar cyanine dyes, styryl dyes, hemicyanine dyes, oxonol dyes, hemioxonol dyes, etc. can be used.

The sensitizing dye used in the present invention is used at a concentration equivalent to that used in ordinary negative-working halogenated emulsions. especially,
It is advantageous to use dye concentrations that do not substantially reduce the inherent sensitivity of the silver halide emulsion.

In the photographic material of the present invention, the photographic emulsion layer and other layers are coated on one or both sides of a flexible support commonly used in photographic materials. Useful flexible supports include films of synthetic polymers such as cellulose acetate, cellulose acetate butyrate, polystyrene, and polyethylene terephthalate.

In the photographic material of the present invention, the photographic emulsion layer and other hydrophilic colloid layers can be coated on the support or on other layers by various known coating methods. For coating, a dip coating method, a roller coating method, a curtain coating method, an extrusion coating method, etc. can be used.

Regarding these photographic additives, supports, manufacturing methods, etc., please refer to the aforementioned Research Disclosure Vol. 176, 22-31.
It is written on the page.

The present invention can be used for any photographic material. For example, it is used in X-ray photographic window optical materials, lithographic photographic materials, black-and-white negative photographic materials, and the like.

For photographic processing of the light-sensitive material of the present invention, for example, Research Disclosure,
re) No. 176, pages 28-30 (RD-17643
) Any of the known methods and known treatment liquids can be applied. The processing temperature is usually selected between 18°C and 50°C, but it may also be lower than 18°C or higher than 50°C.

The developer used in black-and-white photographic processing can contain known developing agents. As developing agents, dihydroxybenzenes (e.g. hydroquinone), 3-
Pyrazolidones (e.g. 1-phenyl-3-pyrazolidone), aminophenols (e.g. N-methyl-P
-aminophenol), etc. can be used alone or in combination. For photographic processing of the light-sensitive material of the present invention,
It is also possible to process with a developer containing imidazoles as a silver halide solvent as described in JP-A-57-78535. Further, processing can be carried out using a developer containing a silver halide solvent and an additive such as indazole or triazole as described in JP-A-58-37643. Developer solutions generally contain other known preservatives, alkaline agents, and PHI.
It contains a buffering agent, an anti-fogging agent, etc., and may further contain a solubilizing agent, a toning agent, a development accelerator, a surfactant, an antifoaming agent, a water softener, a hardening agent, a viscosity imparting agent, etc., if necessary.

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 developing method using an automatic developing machine in the present invention includes U.S. Patent No. 3,025,779, U.S. Pat.
No. 556, No. 3,573,914, No. 3,647
, No. 459, British Patent Box 1°269.268, etc., is preferably used.

The developing temperature is 18°C ~ 50'C1, especially 30°C ~
The temperature is preferably 45°C, and the developing time is preferably 5 seconds to 40 seconds, particularly 5 seconds to 25 seconds.

The entire development process from the start of development to the end of fixing, water washing, and drying is preferably 15 seconds to 200 seconds, particularly 20 seconds to 60 seconds.

There are no particular restrictions on the various additives, development methods, exposure methods, etc. of the photosensitive material of the present invention.
February) and Volume 184 Item 18431 (1979
(August 2013) can be referred to.

(Example) 5 g of potassium bromide, 25.6 g of gelatin, 110 thioether (Cllz) zS (C) Iz) 2S (C
H2) Add 2.5cc of 5% water) solution of zOH66
Add 8.33 g of silver nitrate into the solution kept at °C while stirring.
with an aqueous solution of 5.94 g of potassium bromide and 0.726 g of potassium iodide.
An aqueous solution containing g was added in 45 seconds using a double jet method. Subsequently, 2.9 g of potassium bromide was added, then an aqueous solution containing 8.33 g of silver nitrate was added over 24 minutes, and 0.0 g of thiourea dioxide (structure below) was added. 1 mg was added.

After this, 25% ammonia volume 1120cc, 50%N
After adding 10 cc of 114NO and physically ripening for 20 minutes, 240 cc of IN sulfuric acid was added to neutralize. Subsequently, a mixed solution of potassium bromide and potassium iodide was added to an aqueous solution of 153.34 g of silver nitrate and an aqueous solution of potassium bromide over a period of 40 minutes during control double jet operation while maintaining the potential pAg at 8.2. By changing the amount of potassium iodide during this control double jet, the final total iodine content was changed. 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 the addition was completed, 15 cc of 2N potassium thiocyanate solution was added, and then 45 cc of 1% potassium iodide aqueous solution was added.
cc was added over 30 seconds. After that, increase the temperature to 35°C
After removing soluble salts by sedimentation method,
The temperature was raised to 76 g of gelatin, 76 g of Proxel and 760 g of phenoxyethanol were added, and the pH was adjusted to 6.50 and pAg to 8.20 with caustic soda and potassium bromide.

After raising the temperature to 56°C, 186 μ of 4-hydroxy-6-methyl-1,3,3a,7-titrazaindene was added, and 10 minutes later, 520 μ of the sensitizing dye (the following structural formula) was added.
Added. After another 10 minutes, sodium thiosulfate pentahydrate 3.4 ■ thiocyanic acid 140 mg, chloroauric acid 3.1
(2) was added to the emulsion, and 70 minutes later, it was rapidly cooled and solidified to form an emulsion.

(CH2)3' (CH2)xSO,
+Na sO + In the obtained emulsion, 99.5% of the total projected area of all grains consists 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 is 1.48 μm, standard deviation. 2
5.6%, the average thickness was 0.195 μm, and the aspect ratio was 7°6. The total iodine content was 3.2 mol% based on the total silver amount.

The following chemicals were added per mole of silver halide to the iI+ emulsion of Agent 1'- to prepare a coating solution.

・Polymer latex (poly(ethyl acrylate/methacrylic acid)-97/3) 25.0g ・Hardening agent 1.2-bis(sulfonylacetamido)ethane 3.0g ・2.6-bis(hydroxyamino)-4- Diethylamino 1.3.5-) riazine 80 ■ Sodium polyacrylate (average molecular weight 4,10,000) 4.0 g Potassium polystyrene sulfonate (average molecular weight 600,000) 1.0 g Polyacrylamide (average molecular weight 4,5 10,000) i of 24g゛-H
. (2) Preparation of emulsion Compound (1) was dissolved in tricresyl phosphate and emulsified and dispersed in an aqueous gelatin solution to prepare an emulsion.

(2) Preparation of Emulsion-B Compound (4) was dissolved in tricresyl phosphate and emulsified and dispersed in an aqueous gelatin solution to prepare an emulsion.

(2) Emulsion-A and Emulsion-B were further added to a solution having exactly the same composition as the emulsion coating solution-(1).

The amount added is 600 ■Compound (1) (Emulsion-A) per mole of silver halide.
4) (Emulsion-B) 500 mg.

U on the right - Preparation of emulsion-C Compound 021 was dissolved in tricresyl phosphate and emulsified and dispersed in an aqueous gelatin solution to prepare an emulsion.

(2) Preparation of emulsion-D Compound 03) was dissolved in tricresyl phosphate and emulsified and dispersed in an aqueous gelatin solution to prepare an emulsion.

(2) Emulsion-0 and Emulsion-D were further added to a solution having exactly the same composition as the emulsion coating solution (1).

The amount added is compound-〇2) (emulsion-〇) 500■ compound- per mole of silver halide.
03) (Emulsion-D) 600■.

1st Part ■I1 ■Preparation of Emulsion-E Compound 09) was dissolved in tricresyl phosphate and emulsified and dispersed in an aqueous gelatin solution to prepare an emulsion.

(2) Preparation of emulsion-F Compound (2I) was dissolved in tricresyl phosphate and emulsified and dispersed in an aqueous gelatin solution to prepare an emulsion.

(2) Emulsion-E and Emulsion-F were further added to a solution having exactly the same composition as the emulsion coating A(+) described above.

The amount added is Compound-Og) (Emulsion-E) 500■ Compound-Q per mole of silver halide
O (emulsion-F) is 600 ■.

Preparation of Support A transparent polyethylene terephthalate base having a thickness of 175 μm was provided with an undercoat layer on both sides in the following coating amount.

・Gelatin 84mg/Bo17
1g/pom fee! 1 Printing 1 (a) The emulsion coating solution-1 was coated on the above-mentioned double-sided undercoated base at the same time as the surface protective layer coating solution to obtain a photosensitive material-I.

The applied SN amount was 1.85 g/nf per side, and the coating was applied to both sides.

The coating amount of each component on the surface protective layer was adjusted as shown below.

Table a Hankyu 2 1 Fabric weight Gelatin 1.15g/n (Polyacrylamide (average molecular weight 45,000) 0.25 Sodium polyacrylate (average molecular weight 400,000) 0.02 p-m-octyl Sodium salt of phenoxydiglyceryl butyl sulfonate 0.02 ・Poly(degree of polymerization 10) oxyethylene cetyl ether 0.035 ・Poly(degree of polymerization 10) oxyethylene-poly(degree of polymerization 3) oxyglyceryl-p-octyl phenoxy ether 0.01 ・4-hydroxy-6-methyl 1.3.3a,7-chitrazaindene 0.0155 ・2-chlorohydroquinone 0.154g・CF+7SO
3Ko, OO3 C3Hfu・CaF+tSOiN −(−CHzCIlzO し「+
C1l z-catty5OJa0.001 CJ?・CsF + tsOzN + CHzCIlzO+η
0.025 Poly(
Methyl methacrylate/methacrylate) (molar ratio 7:3, average particle size 2.5 μm) 0.020 (b) Each of the above emulsion coating liquids -■ ~ (rV) were used, and the photosensitive materials were
Coating was carried out in exactly the same manner as in 1 to obtain photosensitive materials - (II) - (
rV) was obtained.

The amount of gelatin coated on photosensitive material-1 was 2.55 g on one side, and the amount of gelatin coated on photosensitive materials -(n) to (rV) was 2.5 g on each side.
．． It was 65g.

Buddha 1'') L Developer solution Part A' Potassium hydroxide Potassium sulfite Sodium sulfite Potassium carbonate Borate Diethylene glycol Diethylene triamine Pentaacetic acid 3.31-Dithiobishydrocinnamic acid 5-Methylbenzotriazole Hydroquinone Potassium bromide 30g 30g 40g 0g 5g 80g 2g 2g 6g g g 2g 0g g g 0.2g 0.225 g 0.015 g 450 g 30 g 15g Ig Part B Triethylene glycol 25g 5g Glacial acetic acid 5-nitroindazole l-phenyl-3-pyrazolidone 102. 6g 3.75g 34.4g 7.6g (90χ) 0.25g 2.3g Part C Glutaraldehyde (50wt/wtχ) Potassium metabisulfite 50g 50g 0g 0g Add starter glacial acetic acid potassium bromide water and 7g 00g 2000IR1 Constant λL1■ Ammonium thiosulfate (70wt/Sio1χ)00I1
1 Rum trihydrate 0.03g Sodium thiosulfate/natural water salt 10g Sodium sulfite
25g boric acid
4g tartaric acid
3.2g glacial acetic acid 31.5g
Sodium hydroxide 1g sulfuric acid (
36N) 3.9g aluminum sulfate 10g1 (N,N-dimethylamino) ethyl-5-mercaptotetra V') Lt 1g in water 400dpH4,6
5 The developer concentrate was filled into a polyethylene container for each part. In this container, the containers of parts A, B, and C are connected together.

The above fixer concentrate was also filled into a polyethylene container.

Ethylenediaminetetraacetic acid/nitriacetic acid These developer and fixer were filled in the developing tank and fixer tank of an automatic processor in the following proportions using metering pumps installed in the automatic processor.

Developer Solution Fixer Solution (pH 10,50) 300 ml of starter was added to the developer tank. Fill the washing tank with tap water, and place it at the bottom of the tank.
Four bags containing 50 g of a silver sustained release agent containing 0.5% (wt) Ag2O [trade name Biosure SG (manufactured by Kinki Pipe Giken)] were submerged in meltable glass consisting of NazO/BzOs/SiO2 and wrapped in non-woven fabric. Ta.

The photosensitive materials (1) to (IV) were exposed to X-rays using a screen HR-4 manufactured by Fuji Photo Film Co., Ltd., and processed according to the processing time described above.

The results are as follows. Measured with Macbeth's TR-927
It was measured using visual density.

□□□□] Procedural Amendment Photosensitive Material-1 The silver color tone is yellowish, while the color tones (II) to (IV) have a preferable cool black tone with an increased bluish tone. Indicated.

The relative sensitivity of Umbrella Photosensitive Material-1 is set to 100.

Umbrella wheel Cuff+0.25 to Cuff+2.0 gradation l
.

2゜ 3゜

Claims (1)

[Scope of Claims] 1) In a silver halide photographic light-sensitive material having at least one silver halide photographic emulsion layer on at least one side of a support, in the silver halide emulsion layer and/or other layers. A halogenated silver image with improved tone, characterized in that the dye image compatible with silver development is formed by a non-diffusible compound that loses its ability to release a diffusible dye upon oxidation. Silver photosensitive material. 2) According to claim 1), the color image density formed by the non-diffusible compound which loses its ability to release diffusible dyes upon oxidation is 1/10 or less of the corresponding silver image density. The silver halide photographic material described above.