JPS60158436A - Black-and-white photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a black-and-white photographic sensitive material having a reduced yellow tone by forming a photographic silver halide emulsion layer contg. flat platelike silver halide particles as the principal component on a base and by incorporating an optical whitening agent into the emulsion layer or other hydrophilic colloidal layer. CONSTITUTION:A photographic silver halide emulsion layer contg. flat platelike silver halide particles whose diameter is >=5 times the thickness by >=50% of the total projection area of all of silver halide particles is formed on a base. An optical whitening agent such as a compound represented by formula I or II is incorporated into the emulsion layer or other hydrophilic colloidal layer to obtain the desired black-and-white photographic sensitive material. The emulsion contg. flat platelike silver halide particles is prepd. by forming seed crystals contg. >=about 40wt% flat platelike particles in an atmosphere having <=1.3pBr and relatively high pAg and by simultaneously adding silver and a halogen soln. while keeping the pBr value so as to grow the seed crystals.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide black-and-white photographic light-sensitive material, and more particularly, it relates to a silver halide black-and-white photographic material with improved color tone containing tabular silver halide grains. It relates to photographic materials.

(Prior art) In recent years, covering power (blackening density/developed silver amount) has been improved by using shaped silver halide grains (for example, those whose grain diameter is j times or more the grain thickness) in silver halide black-and-white photographic light-sensitive materials. often improves.

Emulsions containing tabular silver halide grains provide very high covering power when developed, as mentioned above, because of their large projected area compared to emulsions containing grains of other shapes of the same volume. On the other hand, because the grains are thin, the absorption wavelength of the developed silver becomes shorter and the absorption of blue light increases, so the color tone of the developed silver becomes reddish and strongly yellowish. Such an effect is remarkable when observing using reflected light.

Such a yellowish color of developed silver is not desirable in black and white photographic materials, which are products in which the developed silver is directly observed as an image. For example, in the case of a medical X-ray film, it may be observed not only by transmitted light but also by reflected light, so such a yellowish image silver color gives an unpleasant impression to the observing eye.

In order to change the color of developed silver, it is common practice to use something called a color toning agent.

For example, mercapto compounds are known as color toning agents, and specifically include the following.

However, even if such a well-known color toning agent is applied to a photographic emulsion containing tabular silver halide grains, the color tone of developed silver under a reflected light source will not be improved much. , cannot be used because it causes a significant desensitization effect.

(Object of the Invention) Therefore, an object of the present invention is to provide a black-and-white photographic material containing tabular silver halide grains with improved color tone (reduced yellow tinge). Another object of the present invention is to provide a black-and-white photographic material containing tabular silver halide grains with improved color tone without significant desensitization.

(Structure of the Invention) The above object of the present invention is to provide a black and white photographic material having a support and at least one silver halide emulsion layer.
The silver halide emulsion layer is composed of a silver halide photographic emulsion in which tabular silver halide grains having a grain size of at least j times the grain thickness occupy 10% or more of the projected area of all silver halide grains, and This can be effectively achieved by incorporating a fluorescent brightener into the silver halide emulsion layer or other hydrophilic colloid layer.

The fluorescent brightener used in the present invention includes K,
“The Chemis” edited by Veenkataraman
Compounds listed in Chapter g of Volume V of "TRY OF 8 SYNTHETIC DYES" can be used. Specifically, stilbene compounds, coumarin compounds,
Examples include biphenyl compounds, benzoxacylyl compounds, naphthalimide compounds, pyrazoline compounds, and carbostyryl compounds.

One agent is preferably used. (This is preferable because it does not cause visible coloration such as yellow due to absorption and emits blue light that cancels out the yellowish tinge.) The fluorescent brightener used in the present invention is a water-soluble one that can be used directly. It can be added to photosensitive materials as an aqueous solution. It is also possible to use it by adding it to the processing solution. In the case of a water-insoluble fluorescent brightener, it can be dissolved in a high-boiling organic solvent and added to the light-sensitive material. Water-insoluble fluorescent brighteners are preferred from the standpoint of improving color tone. Specific compounds are listed below, but the present invention is not limited to these compounds.

When adding a water-insoluble fluorescent whitening agent, As mentioned above, a high boiling point organic solvent is used, and specifically, for example, the method described in US Pat. No. 322,027 is used. For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate), phosphoric acid esters (diphenyl phosphate, trinoenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (e.g. acetyl trizotyl citrate) , benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, diethyl azelate), trimesic acid esters (e.g. tributyl trimesate), etc., or boiling point In combination with an organic solvent at about 3°C to 60°C, such as lower alkyl acetate such as ethyl acetate and butyl acetate, ethyl propionate, secondary butyl alcohol, methyl in butyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc. After dissolving it, it is dispersed in a hydrophilic colloid and used as an emulsion.

When the fluorescent brightener of the present invention is added to a photographic material, it is applied to an emulsion layer such as a tabular silver halide emulsion layer, an intermediate layer, a protective layer, and other hydrophilic colloid layers.

The amount of the fluorescent brightener of the present invention to be added is /×l0-3~
2×10 mol 1 mol Ag (tabular silver halide) is preferred, especially co×10 to 1×10 −2 mol 1 mol Ag
(Tabular silver halide) is preferred.

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

In the tabular silver halide grains used in the silver halide emulsion of the present invention, the grain size is equal to the grain thickness! more than twice, preferably j to ioo times, more preferably 3 to 5 times
0 times, particularly preferably r to 30 times. Also, what is the allocation of tabular silver halide grains in the projected area of all silver halide grains? 0chi or more, but preferably 70
% or more, particularly preferably is% 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 O0! ~
10μ, preferably O, O~j, Oμ, particularly preferably l-jμ. The thickness of the particles is preferably 00.2 μm or less.

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. Further, the grain thickness is expressed as the distance between λ parallel planes constituting the tabular silver halide grain.

In the present invention, more preferred tabular silver halide grains have a grain diameter of o, 4 μm or more, j, 0 μm or less, a grain thickness of O″: 2 μm or less, and average diameter/average thickness! or more! O or less.More preferably, grains having a grain diameter of 1.0 μm or more and 5.0 μm or less and a diameter/thickness of ♂ or more occupy 11 or more of the total projected area of all silver halide grains. This is the case with silver photographic emulsions.

The tabular silver halide grains may be any of silver chloride, silver bromide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide;
Silver iodobromide and silver chlorobromide with silver iodide/J molt or less or silver chloride with a content of 0 mol% or less, silver chloroiodobromide and silver chlorobromide with a silver iodide content of 2 mol% or less are more preferable, and in mixed silver halides. The composition distribution may be uniform or localized, but uniformity is preferable. Further, the particle size distribution may be narrow or wide.

The tabular silver halide emulsion is from Cugnac.

Chateau's report and Duffin, “Photo
graphics mulsion chemistry
”, Focal Press.

New York, / AA, p, tA ~72, and A, P,) (, Trivelli, W, F, Sm1
Th.

Phot, J,,za0,. 21j(/?1AO)Il'
Although it is listed as C, it is published by Tokukai Sho! r-/, 27. ri2/,
Tokukai Akira! ;l-113,927,% Kaisho 3g-//3.
It can be easily prepared by referring to the method described in 22g.

For example, in an atmosphere with a relatively high pAg value of pBr/3 or less, seed crystals containing tabular grains of 11-0% or more by weight are formed, and silver and halogen solutions are simultaneously added while keeping the pBr value at the same level. It can be obtained by growing seed crystals.

During this grain growth process, it is desirable to add a silver and halogen solution to prevent the generation of new crystal nuclei.

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 the solvent used is preferably 10 to 10% by weight, particularly 10 to 10% by weight of the reaction solution.

For example, as the amount of solvent used increases, the particle size distribution can be made monodisperse, and the growth rate can be completely accelerated. On the other hand, there is also a tendency for the thickness of the particles to increase with the amount of solvent used.

Often used silver halide solvents include ammonia, thioethers and thioureas. Regarding thioethers, US Patent No. J, 27/
, No. 167, No. 3, 7ri θ, No. 3g7, No. 3. j7
≠, No. 62j, etc. can be referred to.

In the process of silver halide grain formation or physical ripening,
Cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts thereof, rhodium salts or complex salts thereof, iron salts or iron complex salts, etc. may all coexist.

During the production of the tabular silver halide grains of the present invention, the addition rate, amount, and additive IJ [I A method of increasing ae is preferably used.

Regarding these methods, for example, British Patent No. 1゜33j,
2nd issue, U.S. Patent No. 3. Otsu 72. ri Q0, same No. 3.
AjO, No. 717, No. ≠, No. 21A, No. J, Hiroshi No. J, No. 717, No. ≠ λ3, No. J! -/! You can refer to the descriptions in I/2≠ issues, etc.

The tabular silver halide grains of the present invention can be chemically sensitized if necessary.

For chemical sensitization, for example, H0Frieser edition Di
e Grundlagen der Photogra
phischenProzesse mit Silb
Erhalogeniden (Akademische
V'erlagsgesellschaft.

The method described in Ili Af), 47j-73 I/L Tei 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 sensitization method using amines, hydrazine derivatives, formamidine sulfinic acid, 7 run compounds); noble metal compounds (e.g. total complex salts,
Pt.

A noble metal sensitization method using complex salts of metals of group (I) of the periodic table such as Ir and Pd can be used alone or in combination.

Specific examples of these include U.S. Patent No. 1 for sulfur sensitization.
．． j7'A, ri++ No. 2. 'A10゜/, No. 19, No. 1, 27g, No. 9≠7, No. λ.

721, At, No. g, same No. 3. U.S. Patent No. 2,913,602, U.S. Patent No. 411F, U.S. Pat.
For precious metal sensitization methods such as rt No. 2, U.S. Patent No. 2, 3 Tata, 0za No. 3, U.S. Patent No. 3, z, φV? .

It is described in the specifications of British Patent No. 010, British Patent No. O/♂, No. 067, etc.

Particularly from the viewpoint of saving silver, the tabular silver halide grains of the present invention are preferably gold-sensitized, sulfur-sensitized, or a combination thereof.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing capri during the manufacturing process and storage of the light-sensitive material, or for stabilizing the photographic performance. That is, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, chromobenz-midazoles, mercaptothiazoles,
Mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (%/-phenyl-j-mercaptotetrazole), etc.; mercaptopyrimidines; mercaptotriazoles dinos; thioketo compounds such as oxtedrynthion; niazaindenes, such as triazaindenes, tetraazaindenes (particularly ≠-hydroxy-substituted (/, 3.3a, 7) tetraazaindenes), pentaazaindenes; A number of compounds known as anti-capri agents or stabilizers can be added, such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, and the like.

For more detailed examples of these and how to use them, see, for example, US Patent No. 3. rij≠, No. 17μ, same 3. Is it written in Ir2, 94L7, '4 Kosho I2-, 2t, Otsu 2θ? Can be 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 sorbitan esters, polyalkylene glycols Non-ionic materials such as alkylamines or amides, polyethylene oxide adducts of silicone), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, ayagylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Surfactant; alkyl sulfonate, alkyl sulfonate, alkylbenzene sulfonate, alkylnaphthalene sulfonate, 'alkyl sulfate, alkyl phosphate, x, ffi, N-azole-N-alkyl taurine , sulfosuccinates, sulfoalkyl polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphates, etc., and hostile groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, etc. τ anionic surfactant;
Ampholytic surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphoric acid esters/v, alkyl betaines, amine oxides; alkyl amine salts, aliphatic or aromatic ≠ primary ammonium salts, pyridinium, Cationic surfactants such as complex μ-class ammonium salts such as imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used.

The photographic emulsion layer of the photographic light-sensitive material of the present invention contains, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, and thiomorpholine for the purpose of increasing sensitivity, increasing contrast, or promoting development. , tetravalent ammonium salt compounds, urethane derivatives,
It may also contain urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like. For example, US Patent Co., ≠00. jf
No. 3.2, same λ, ll-23. ! Geta, λ, 7/Otsu, Oz 2, 3. t/7,2. ! rO No. 3,77
2゜0.2/No. 31go and No. 003, British Patent/
.

Those described in ≠rr, Tata/No., etc. can be used.

The photographic light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer in the photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability. For example, alkyl (meth)acrylate, alkoxyalkyl (meth)acrylate, glycidyl (meth)acrylate, (meth)acrylamide, vinyl ester (for example, vinyl acetate), acrylonitrile, olefin, styrene, etc. alone or in combination, or these and acrylic Polymers containing a combination of acids, methacrylic acid, α, β-unsaturated dicarboxylic acids, hydroxyalkyl (meth)acrylates, sulfoalkyl (meth)acrylates, styrene sulfonic acids, etc. as monomer components can be used.

The photographic material of the present invention may contain an inorganic or organic hardening agent in the photographic emulsion layer or other hydrophilic colloid layer. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, geltaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylo-,-dimethylhydantoin, etc.), dioxane derivatives (2,3 -dihydroxydioxane, etc.), 7-active vinyl compounds (1,3,j
-) lyacryloyl-hexahydro-8-)! Jacin, /, j-vinylsulfonyl-2-propatur, etc.), active halogen compounds (2,≠-dichloro-t-hydroxy-8-triazine, etc.), mucohalogen 1li (
mucochloric acid, mucophenoxychloric acid, etc.), etc. can be used alone or in combination.

In the photosensitive material produced using the present invention, when the hydrophilic colloid layer contains dyes, ultraviolet absorbers, etc.
They may be mordanted, such as by cationic polymers.

A photosensitive material produced using the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful.

The photographic emulsions used in the present invention may be spectrally sensitized with methine dyes and others. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxynol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, viroline nucleus, oxazinone nucleus, thiacillin nucleus, virol nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus,
Pyridine nuclei, etc.; Nuclei in which fatty hydrocarbon terms are fused to these nuclei; and nuclei in which aromatic hydrocarbon rings are fused to these nuclei, sokuchi, indolenine nucleus, benzindolenine nucleus, indole nucleus, benz Oxadole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus, etc. are applicable. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes include a pyrazoline-yone nucleus, a thiohydantoin nucleus, a 2-thioxazoline-2,
J to 6-membered heterozygotes such as Hiro-dione nucleus, thiazolidine-2,≠-dione nucleus, rhodanine nucleus, thiobarbital acid root, etc. can be applied.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion. for example,
Aminostyl compounds substituted with nitrogen-containing heterocyclic groups (for example, U.S. Pat.
72/), aromatic organic acid formaldehyde condensates (such as those described in US Pat. No. 3,7≠3,610), cadmium salts, and the like.

Various other additives may be used in the silver halide photographic emulsion of the present invention or a light-sensitive material using the same. For example, desensitizers, matting agents, development accelerators, oils, mordants, ultraviolet absorbers, etc.

Regarding the aforementioned items and these additives, please refer to Research Disclosure (RE8EARCHDISC).
LO8URE) / Issue 74, pages 22-31 (R, D
-/74113) (Dec,,/7F), etc. can be used.

In the silver halide photographic emulsion used in the present invention, in addition to gelatin, protective colloids include acylated gelatin such as heptatalized gelatin and malonated gelatin, cellulose compounds such as hydroxyethyl cellulose and carboxymethyl cellulose; Soluble starches such as polyvinyl alcohol, polyvinylpyrrolidone, hydrophilic polymers such as polyacrylamide and polystyrene sulfonic acid, plasticizers for dimensional stabilization, latex polymers and matting agents may be added. Completion (fini)
shed) The emulsion is coated onto a suitable support.

As a support, polyalkyl (meth)acrylate,
polyesters such as polystyrene, polyvinyl chloride, partially formalized polyhinyl alcohol, polyesters, or polyethylene terephthalate;
or a film made of a synthetic polymer such as polyamide; a film made of a cellulose derivative such as cellulose nitrate, cellulose acetate, or cellulose acetate-butyrate;
Any of the transparent or opaque supports commonly used in photographic elements can be used, such as paper, baryta-coated paper, paper coated with alpha-olefin polymers and the like, synthetic paper such as polystyrene, and the like.

Specifically, the black-and-white photographic materials of the present invention include X-ray photographic materials (for direct use and indirect use), black-and-white photographic paper, computer typesetting film, or photographic paper, as well as black-and-white photographic materials,
Examples include photosensitive materials for plate making.

Photographic processing of layers comprising the photographic emulsions of the invention may be carried out, for example, by using Research Disclosure.
closure) / 7 A whistle 21-30 (R
D-/7A≠3) Any of the known methods and known treatment liquids can be applied.

The processing temperature is usually chosen between it 0C and jooC, but may be warm below 1t 0C or above so 0C.

The developer used in black-and-white photographic processing can contain known developing agents. As developing agents, dihydroxybenzenes (for example), hydroquinone), 3
-pyrazolidones (e.g. /-phenyl-3-pyrazolidone), aminophenols (e.g. N-methyl-
p-aminephenol), etc. can be used alone or in combination. The developer generally contains other known preservatives, alkaline agents, pH buffers, antifoggants, etc., and, if necessary, solubilizers, color toning agents, development accelerators, etc.
It may also contain a surfactant, an antifoaming agent, a water softener, a hardening agent, a viscosity imparting agent, and the like.

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.

Example 1 Photographic material/~g was created as follows.

309 g of gelatin in 1 liter of water. Potassium bromide 10.3f, 0,
6wt% thioether (HO(CH2)2S(CH2)2S(CH2)20H
) in a container containing 10 cc of aqueous solution and maintained at 700C (pA
The following solution I and [f:/ were added simultaneously to the solution I and [f:/] for 6 seconds while stirring, and then solutions ① and ① were added simultaneously by the double jet method over 65 minutes.

Furthermore, while the solutions (2) and (2) were being added, the solution (2) was added simultaneously over a period of 75 minutes.

The obtained tabular silver halide grains had an average diameter of 2.0
μ, the average diameter/thickness ratio is 16, and silver iodide is 0θ
It was morchi. After chemical sensitization using gold and sulfur sensitization, sensitizing dye (ndium 3-[j-chloro-λ-
(2-(j-chloro-J-(3-sulfonatepropyl)benzoxazoline-λ-ylidenemethyl)-/-
butene)-3-penzoxazino]pronoξsulfonate, an antifoggant (≠-hydroxy-6-methyl-/, 3.3a, 7-chitrazaindene), and a thickener (polypotasium p-vinylbenzene sulfonate). This was added to prepare a coating solution. At this time, the weight ratio of silver/gelatin was /, θj.

To the above tabular silver halide emulsion, as shown in Table 1, a toning agent for comparison and a water-soluble fluorescent whitening agent of the present invention were respectively added to both sides of a polyethylene terephthalate support. Photographic material/~g was prepared by coating and drying simultaneously with the surface protective layer. In addition to gelatin, the surface protective layer contains a thickener, sodium polystyrene sulfonate, and fine particles of polymethyl methacrylate (average particle size: 3.0 μm).
, a hardening agent N, N'-ethyl V-bis(vinylsulfonylacetamide) and a coating aid sodium t-octylphenoxyethoxyethoxyethanesulfonate were used in a 10 wt % gelatin solution in water. The amount of coated silver in the layer is 2.397m per side.
The amount of gelatin applied in the surface protective layer is /, 397m2
The thickness was 1.08 m. 2s' of these samples
All samples were tested 7 days after application while maintaining the temperature and humidity of CXAj%R,H. 2! It has an intensity peak at nm! After exposure to 00-1.10 nm green light, the following processing was performed.

Processing A: After developing for 3s'c and 2s with a developer with the following formulation, 3j 0C12! with a fixer with the following formulation.
It was fixed for seconds, washed with water and dried.

Developer A /-Phenyl-3-pyrazolidone /, 39 Hydroquinone 301i' Nitroindazole 0.23? KBr 3.7f Anhydrous sodium sulfite s, oy Potassium hydroxide 20f Boric acid iol, 26% glutaraldehyde aqueous solution Add 20ml of water to bring the total volume to /l.

(pH was adjusted to io,,zo) Fixing solution Ammonium thiosulfate 200.0'i Sodium sulfite (anhydrous) 20.0y Boric acid, r, of/ Ethylenediaminetetraacetic acid disodium trilum O,/7 Aluminum sulfate is, oy Sulfuric acid ,oy Glacial acetic acid 22+oy Add water / ,01 (pH is adjusted to ≠, 0) Perform sensitivity measurements on the processed photographic material and use the results as the first
Shown in the table. Here, the sensitivity jf value is calculated as the logarithm of the reciprocal of the exposure amount necessary to obtain the degree of transmitted light blackening of the fog value 0/, θ, and it is expressed as a relative value with the sensitivity of the tabular emulsion without additives as ioo. displayed. At the same time, we calculated the maximum transmitted light density (Dmax) for the coated silver amount per j g. Also, for the same developed sample, the reflection a degree (reflection density due to back-colored light when the appropriate density is approximately 1) was determined. DG, DB) were measured and the color tone of the developed silver was observed, and the results are also listed in Table 1.

From the results in Table 1, it can be seen that the color tone of the tabular grains from the sample is black with a yellowish-reddish tinge.

Moreover, in samples 2 to 3 containing a color toning agent, not only the yellowish tone of the color tone was hardly reduced, but also the sensitivity was significantly lowered.

In contrast, sample j containing the fluorescent brightener of the present invention
-f, surprisingly the yellow color of the hue could be significantly reduced with little loss of sensitivity.

Example 2 Additives below the sensitizing dye were added to a tabular emulsion prepared in the same manner as in Example 1, a surface protective layer was applied, and samples were prepared as shown in Table 2. )It was created. However, since the fluorescent brightener used as an additive in this example is water-insoluble, it is dissolved in a high-boiling solvent, and then dispersed in a gelatin shell using a surfactant to create a protective layer. Added to. These coated samples were 2r'c,t
Seven days after application while maintaining the temperature and humidity of s%R)f, each sample has an intensity peak at j2jnm!
After exposure to green light of 00-10 nm, the same treatment as in Example 1 was carried out, and the results are summarized in Table 2.

According to the results in Table 2, it can be seen that the color tone of the tabular grains from the sample is black with a yellowish-reddish tinge.

Further, in samples λ to j containing a color toning agent, not only the yellowish tone of the color tone was hardly reduced, but also the sensitivity was significantly lowered.

In contrast, Sample 6 containing the fluorescent brightener of the present invention
Surprisingly, the yellow color of the color tone was significantly reduced and the color tone could be made more bluish with almost no decrease in sensitivity.

Patent Applicant Fuji Photo Film Co., Ltd. Procedural Amendment Showa J! 7th Year 7-Mitsubishi-1 Mr. Commissioner of the Japan Patent Office 1, Indication of the case 1920, Showa J. Pat. Person 4, Subject of amendment The description in the "Detailed Description of the Invention" column 5 of the description and the "Detailed Description of the Invention" section of the description of the amendment shall be amended as follows.

/) Page 41 is the line Delete "logarithm of".

j) No. μ/page 2nd line Delete all "coated silver amount is 51 pieces".

3) Table 1 on page 1/-2 ``(Development Gin μ, Otsu 2 Todoroki)'' is deleted.

l) Table 2 on page 41 “(Development silver, z2,!7) Delete J.

Procedural amendments Showa to Lambda 7, 2016, Director General of the Patent Office, i-iku 1, case display Showa! Patent Application No. 1.27Aj No. 2
Title of the invention Black-and-white photographic material 3, Relationship with the person making the amendment Patent applicant Address 210-4 Nakanuma, Minamiashigara City, Kanagawa Prefecture Subject of the amendment Column 5 of "Detailed Description of the Invention" of the specification, Contents of the amendment The statement in the "Detailed Description of the Invention" section of the specification is amended as follows.

1) Structural formula on page 15 l-18 " and correct it.

2) Structural formula on page 16, line 1-19 and correct it.

Claims (1)

[Claims] In a black-and-white photographic light-sensitive material having a support and at least one silver halide emulsion layer, the silver halide emulsion layer comprises tabular silver halide grains having a grain size of at least j times the grain thickness. A silver halide photographic emulsion that occupies 60% or more of the projected area of all silver halide grains, characterized in that the silver halide emulsion layer or other hydrophilic colloid layer contains a fluorescent brightener. Black and white photographic material.