JPS6327831A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the titled material having less tendency for generating fog, without accompanying defects such as delaying progress of developing, reducing image density, and softening gradient of the image by incorporating a specific compd. to an silver halide emulsion having a high silver halide content. CONSTITUTION:The titled material contains at least one of silver halide emulsion layer mounted on a substrate. The silver halide emulsion layer comprises the silver halide composed of at least 50mol% silver chloride, and contains a compd. shown by formula I wherein Z<1> is an atomic group necessary to forming a satd. or an unsatd. heterocyclic ring together with a sulfur atom, and the formed heterocyclic ring may be substd. Thus, the generation of the fog particular to the AgCl emulsion is reduced, and delaying the progress of developing and lowering gamma which generates by a conventional antifogging agent are suppressed, and conversely, the good effects for the progress of developing and the gamma are obtd.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a photographic light-sensitive material using a silver halide emulsion, and in particular to a silver halide light-sensitive material suitable for rapid development processing. .

(Prior Art) In recent years, the photographic industry has been eager to shorten access time, and there is an urgent need to develop silver halide photographic materials suitable for rapid processing.

Silver halide emulsions with a high silver chloride content (hereinafter referred to as high silver chloride emulsions) have the fastest development progress among photosensitive silver halides and are suitable for this purpose, but inevitably It has the disadvantage that fog is likely to occur, and fog, sensitivity, and gradation are significantly deteriorated during storage.

Conventionally, in order to especially prevent fogging, l-
Phenyl! -Heterocyclic mercapto compounds such as mercaptotetrazole have been often used, but these mercapto compounds have strong adsorption to silver halide, which delays the progress of development and reduces the maximum density of one image. This tends to cause problems such as gradation and softness of one gradation, and there are many restrictions on use.

To solve these problems, it has been desired to develop a compound that has relatively weak adsorption to silver halide and effectively suppresses fogging.

(Objective of the present invention) The first object of the present invention is to provide a silver halide photographic material comprising high silver chloride and suitable for rapid processing.
Another object of the present invention is to provide a high silver chloride silver halide photosensitive material in which fog is improved without causing problems such as delay in development, reduction in image density, and softening of gradation. It is to be.

As a result of extensive studies, the present inventors have discovered that the above objects can be achieved by incorporating a compound represented by the following general formula (I) into a high silver chloride emulsion.

In the formula, Zl represents an atomic group necessary to form a saturated or unsaturated heterocycle with the sulfur atom.

This heterocycle may have a substituent.

The atomic group represented by -2l here is carbon atoms.

A heterocycle formed from a nitrogen atom, an oxygen atom, and a sulfur atom, and a heterocycle formed from Zl and a sulfur atom is a 3- to ♂-membered heterocycle, and this heterocycle can be fused with another ring to form a fused ring. Good too.

Specifically Tyran. Chetan-thiane, chepin, thiosine, dihydrothiolane, thiophene.

Dihydrothiopyran, μH-thiopyran, 2H-thiopyran, 1,3-thiacyridine, thiazole.

/,! -oxathiolane, 7.3-dithiolane-/, 3
-dithiolane, 7.3-dithiolane, l.

Examples include .mu.m oxathian-/, .mu.m thiazane-/, J-thiazane, benzothiolane, ba/zothian, benzothiasiridine, penzosaxathian, and the like.

As a substituent of a heterocycle formed from Zl and a sulfur atom,
Specifically, a halogen atom (fluorine atom, chlorine atom, bromine atom), an alkyl group (preferably one with carbon number/-20)
, an aryl group (preferably one having A-20 carbon atoms), an alkoxy group (preferably one having 6 to 20 carbon atoms), an aryloxy group (preferably one having 6 to 20 carbon atoms), an alkylthio group (preferably one having 6 to 20 carbon atoms) is the one with carbon number l ~ 'J O)
, an arylthio group f preferably having 4 carbon atoms. 20 things).

Acyloxy group, preferably one having 2 to λ0 carbon atoms),
Amino group (unsubstituted amino, preferably a secondary or tertiary amino group substituted with an alkyl group having ~20 carbon atoms, or an aryl group having J-20 carbon atoms), carbonamide group (
Preferably, an alkylcarbonamide group having 1 to 0 carbon atoms, an alkylcarbonamide group having t to 0 carbon atoms, a ureido group, preferably an alkylureido group having 20 carbon atoms, and O aryl ureido group), carboxy group, carbonate group (preferably alkyl carbonate group with carbon number/~2θ, aryl carbonate group with carbon number 6 to 20), oxycarbonyl group (preferably carbon number/-50 Alkyloxycarbonyl group - carbon number J-5
0 aryloxycarbonyl group), carbamoyl group (
Preferably a C/~20 alkylcarbamoyl group,
arylcarbamoyl group having 6 to 0 carbon atoms), acyl group C preferably a furkylcarbonyl group having 2 to 2 carbon atoms,
C4-20 arylcarbonyl group)-sulfo group,
Sulfonyl group C preferably an alkylsulfonyl group with carbon number/A-20, an arylsulfonyl group with carbon i+ to 20), sulfinyl group (preferably -!L, <F'i carbon number/-,
20 alkylsulfonyl group, arylsulfonyl group with 6 to 0 carbon atoms), sulfonamide group (C), alkylsulfonamide group with carbon number/-20, carbon number J
-20 arylsulfonamide group), sulfamoyl group (preferably h carbon x number t to 20 alkylsulfamoyl group, carbon number t to coo arylsulfamoyl group)
, cyano group, hydroxy group-nitro group, oxo group, thioquine group, imino group, and selenoxo group.

When there are two or more substituents, they may be the same or different.

Furthermore, preferred compounds among the compounds represented by the general formula (1) can be represented by the following general formula fI[).

General formula ((I) In the formula, Z2 represents a sulfur atom, a carbonyl group, and an atomic group necessary to form a saturated or unsaturated heterocycle having VC, ! ~, and this heterocycle has no substituents. Here, the atomic group represented by Z2 and the substituent of the heterocycle formed from Z2, a sulfur atom, and a carbonyl group are Zl represented by the above general formula rI) and a substituent formed from Zl and a sulfur atom. It means the same as the substituent of heterocycle.

n represents 1-3. When n is co or 3, each carbonyl group may be adjacent or non-adjacent.

Specifically, the j-j membered saturated or unsaturated heterocycle represented by the general formula ((I) may include the following.

Among those represented by the general formula (I), particularly preferred are those in which the carbonyl group is linked to a sulfur atom, and the heterocycle is saturated.

Specific examples of the compound of the present invention represented by general formula (I) are shown below.

Compound j Compound IO Compound l Sweet compound 13 Compound 7≠ Synthesis examples of the compounds of the present invention are described below, and some of them are commercially available and can be easily obtained. It is possible.

Synthesis of Compound 3vy of thiourea and ≠7.3t of chloroacetic acid were added to 100g of water and heated to reflux. - hour later, concentrated hydrochloric acid iomt was added and the mixture was further heated under reflux for 4 hours. The reaction mixture was ice-cooled and the crude crystals were collected. Recrystallization from too ml of water gave compound /.

Collection f4c, 2y (t24) Compound Hiro's synthesis of thiourea 22. Add It and 37°jf of ethyl chloroacetate to ethanol/50d - and add 1 ml of sodium acetate.
Then, the mixture was heated under reflux for - hours. The mixture was allowed to cool, and the resulting crystals were washed several times with water to obtain compound μ.

Yield! ? (Part 7) Synthesis of Compound 7 Thiourea 7JS' and r-butyrolactone rtt were dissolved at 310 tttlVc of hydrogen bromide and heated under reflux for 79 hours. After cooling, add 1 part sodium hydroxide/water to 1 part water.
A solution containing ot)mlK was added little by little, and the mixture was heated under reflux for 13 hours. 1 ml of concentrated sulfuric acid was added little by little while cooling on ice. Compound 7 was obtained by removing M with 1 room of ether and distilling under reduced pressure.

b, p, ri0~ri/'C/kojmHg yield 399 (
314) Synthesis of compound IO Org-@5ynth, Co11. Vol, u,
1. (Cyanamide iu synthesized by the method of I!
t and thiosalicylic acid 309 in tetrahydrofuran t07
ttlVc was dissolved and heated under reflux for 70 minutes. The mixture was cooled to 0'C and yellow crystals were collected as F. Salt this crystal #
kj Dissolve in Oml! The mixture was heated to reflux for an hour. After cooling,
The obtained crystals were separated and recrystallized from ethanol to obtain Compound 10.

Revenue! / Ko, t? (pr4s) The amount of the compound represented by the general formula rI) of the present invention is:
per 7 moles of silver halide, coxl0-5 moles ~ jXIO
It can be used in the molar range, λX10' mole ~/
x10-1 mol is particularly preferred.

The compound of the present invention may be added at any time from the time of nucleation of halide steel grains in the production process of silver halide emulsions to just before coating, but it is particularly preferable to add them after grain growth is complete. is preferred. In particular, it is more preferable to add it during and/or after chemical ripening.

Some of the compounds represented by the general formula (Il) of the present invention are, for example, Japanese Patent Application Publication No. 17-197-/l'rOJt,
It is known as 1-2/7 Octopus No. 9, but all of these are particularly useful silver bromide or silver iodobromide, and the latter is also known as *German use. However, silver iodobromide emulsions have increased fog; for these reasons, the usefulness of the silver chloride emulsions of the present invention cannot be immediately compared.

The high silver chloride grains of the present invention have a silver chloride content of at least 5
It refers to something with a mole ratio of 0 or more. Preferably it is 7 molar, more preferably 0 molar, particularly preferably 9 molar or more.

The remainder consists of silver bromide and or silver iodide.

The content of silver iodide is less than 10 moles, preferably less than 10 moles, more preferably less than 3 moles and 1%, preferably less than 1 mole. It is desirable that a layer mainly composed of silver bromide or silver iodide is localized near the surface of the grains.

The average grain size of the highly chlorinated emulsion of the present invention is not particularly limited, but it is preferably a spherical equivalent diameter of 1 volume weighted average. /μ to 3μ, more preferably O12μ to lμ.

The grain shape of the high silver chloride emulsion of the present invention may include, in addition to the popular cube, 1/J-hedron, 4-tetrahedron, 2r-hedron, larger polyhedron, and spherical shape (for example, +C1aes et al., The Journal of Pbotograp).
hic 5science, 2 lJri (1ri7J
L Wyrsch; Ir+ternatiorz
alCongress of Photography
ic 5sciencey1-lJ-12a (lori7♂)
etc.) and even tabular grains C, for example, U.S. Pat.
3 Tade, λ/yo issue, Dohiro, 1700.1743 etc.)
But that's fine.

By using a silver halide solvent during production of the silver halide grains of the present invention, it is possible to control the grain size, grain shape, grain size distribution, and grain growth rate.

Silver halide solvents that are often used include monothiocyanates, thioethers, thioureas, etc., and ammonia can also be used in combination without causing any adverse effects.

For example, thiocyanate (U.S. Pat. No. 2,220).

Refer to 2. ≠μF,! 3≠No. 3゜320
．． 0≦R, etc.), thioether compounds (for example, U.S. Patent No. 3.Core/, lyo7, U.S. Patent No. 3, J7 Hiro, Tco!, U.S. Patent No. J, 7011./30-U.S. Patent No. μ, Kota 7,13
ri No., Hiroshi Dodai, Core 7゜3 Da No. 7, etc.), Thione Compound C Example Ege Tokkai Sho! J-/! 4&J/ri issue, same j3-r2
4c01, No. 11-77737, etc.), amine compound C (for example, JP-A No. 4c01-100717, etc.), etc. can be used.

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

During the production of silver halide grains of the present invention, the addition rate, amount, and concentration of silver salt solution (e.g., λgNo 3 aqueous solution) and halide solution C (e.g., KBr aqueous solution), which are added to accelerate grain growth, are increased. The method is preferably used.

These methods are described, for example, in British Patent No. 1.33! ,
Octopus J, U.S. Patent No. J, 472. ri No. 00, same No. j,
660, 7! No. 7, same No.≠, 2≠ko, lμ! No., Tokukai Akira! J--/≠λ3 Kota, 5r-7zriia, j1-//3?27.

same! r-//J92r issue, same! I-//1931t issue,
same! You can refer to the descriptions in I-///ri-3, etc.

The silver halide grains of the present invention may be unchemically sensitized, but can be chemically sensitized if necessary.

As a chemical sensitization method, there is a so-called gold sensitization method using a gold compound (for example, US Pat. No. 2.≠at, ot).

No. 3,3λo, otr) or iridium, platinum,
Sensitization with metals such as rhodium, noceradium etc. eg US Pat. No. U, 44! r, No. 060, 2, jlt,
No. 2111 - 2. j4J, 2 Co. λ) or a sulfur sensitization method using a sulfur-containing compound (for example, U.S. Pat. No. 2.2 Co. Reduction sensitization method using urea, polyamine, etc. (for example, U.S. Patent No. J, !J'7.150, U.S. Patent No. J'7.150,
! /r, tri No. 2, same 2. 1, octopus J) - or a combination of λ or more of these can be used.

The emulsions of the present invention are preferably spectrally sensitized with methine dyes or the like. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar-cyanine dyes-hemocyanine dyes, styryl dyes, and hemioxonol dyes.

Particularly useful dyes are monocyanine dyes and merocyanine dyes.
and a pigment belonging to complex merocyanine pigments. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, virol nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus-imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.;
Nuclei in which an alicyclic hydrocarbon ring is fused to these nuclei; and a nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, i.e. indolenine nucleus - benzindolenine nucleus, indole nucleus, benzoxadol nucleus, naphtho An oxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, an inzimidazole nucleus, a quinoline nucleus, etc. are applicable. These nuclei may be substituted with VC on carbon atoms.

Merocyanine dyes or composite merocyanine dyes contain pyrazoline as a core with a ketomethylene structure! -on nucleus, thiohydantoin nucleus, cochoxazolidine-2,
It is possible to apply heteroarticulated ring nuclei such as the Hiro-dione nucleus, the thiazolidine-2,4t-dione nucleus, the rhodanine nucleus, and the thiobarbic acid nucleus.

For example, shrimp RESERCHDISCLOURE Item,
The compounds described in /76413, page 23, section (■) (December /971) or the compounds described in the cited literature can be used.

The amount added is tl x 10-' per mole of silver halide.
1×10” moles can be used, but the more preferred silver halide grain size is O1λ~/.

In the case of 2 μm, approximately j×10 to 10” moles is more effective.

The silver halide emulsion prepared according to the present invention can be used in both color photographic materials and black and white photographic materials.

Examples of color photographic materials include color printers, color photographic films, and color reversal films; examples of black and white photographic materials include X-ray films, general photographic films, and printing films. In particular, colors can be preferably used for -nogu-.

There are no particular restrictions on other additives for the photographic material to which the emulsion of the present invention is applied.
) / 7 item / 7ta3 (RD / 74μ
3) and Volume 17 Item 7♂7/1 (RD/17/
6) (The description in D can be used as a reference.

The description of each food additive in RDi'yta3 and RDlr7/lfc is listed below.

l Chemical sensitizer page 23 Right column on the right page 2 Sensitivity enhancer Same as above 3 Spectral sensitizer 1 strength Pages 23-21 Right column on the tar page ~ Color sensitizer
tμ page right column ≠ Brightener −≠
page! Antifoggant, page 2q ~ page 9, right column and stabilizer, page 2j ~ λ, page tμ, page 9, right column ~
Luther dye-purple Page 410 Left margin line absorber 7 Stain inhibitor 2. page right column tjo page left to right column r dye image stabilizer page 21
- Lubricant Core page Tro page right column 12 Coating aid 1 surface 2A-27 pages Same as above Activator/3 Static prevention Core page Same as above Antifoggant other than one of the above additives -
As stabilizers, azoles (e.g. penzothiazoliu salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, nitroindazoles, benzotriazoles, aminotriazoles, etc.); mercapto compounds (
For example, mercaptothiazoles - mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazole M1%/-phenyl-! -mercaptotetrazoles), mercaptopyrimidines, mercaptotriazines, etc.); thioketo compounds such as oxadolinthione; azaindenes (e.g. triazaindenes, tetraazaindenes) with l-hydroxy substitution (/,!, 3a, 7
＞tetraazaindene), pentaazaindene); benzenethiosulfonic acid, benzenesulfinic acid,
Benzene sulfonic acid amide and the like can be preferably used.

The color coupler is preferably a non-diffusible color coupler having a hydrophobic group called a pallast group in its molecule, or a polymerized color coupler. The coupler may be either monomer or di-equivalent to silver ion. It may also contain a colored coupler that has a color correction effect or a coupler that releases a development inhibitor during development (so-called DIR coupler). The product of the coupling reaction may also be colorless and include a colorless DIR coupling compound that releases a development inhibitor.

For example, as a magenta coupler! - pyrazolone coupler, pyrazolobenzimidazole coupler, pyrazolotriazole coupler - birazolotetrazole coupler,
Examples include cyanoacetyl coumaron couplers, open-chain acylacetonitrile couplers, and yellow couplers include acylacetamide couplers C (eg, benzoylacetanilides, pivaloylacetanilides), and the like.

Examples of cyan couplers include naphthol couplers and phenol couplers. As for cyan couplers, U.S. Patent No. 377.2002, U.S. Patent No. 2772142, U.S. Patent No. 3711301-U.S.
No. 11, Doko 327/73 - No. 31 Bow T Coco - Same ≠
333 Tade No. 9, same≠pji jzri No., same μμ core 7
Phenolic couplers having an ethyl group at the meta position of the phenol nucleus described in No. t7 etc., co,! -Diacylamino-substituted phenolic couplers, phenolic couplers with a phenylureido group at the 2nd position and an acylamino group at the 5th position, couplers with a naphthol substituted with a sulfonamide or amide at the 5th position, etc., have improved image fastness. Excellent and desirable.

Two or more types of the above couplers etc. can be used in the same layer in order to satisfy the characteristics required of a photosensitive material, or the same compound can be added to two or more different layers.
Of course it doesn't matter.

As anti-fading agents, hydroquinones, 6-hydroxychromans,! -Hydroxycoumarans, spirochromans, p-alkoxyphenols.

Typical examples include hindered phenols, mainly bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl group of each of these compounds. Can be mentioned. Further, metal complexes such as C bissalicylaldoximad) nickel complex and (bis-N,N-dialkyldithiocarbamado) nickel complex can also be used.

For photographic processing of light-sensitive materials using the present invention, any known method can be used, and known processing solutions can be used. Also, the processing temperature is usually −ir 0
The temperature is selected between c and 50oC, but the temperature may be lower than 1r0C or above jo'c. Depending on the purpose, either a development process C (black and white photographic process) for forming a single silver image, or a color photographic process consisting of a development process for forming a single dye image can be applied.

The black and white developer contains known developing agents such as dihydroxyincenes (e.g. hydroquinone), 3-pyrazolidones (e.g. l-phenyl-3-pyrazolidone), and aminophenol a (e.g. N-methyl-p-aminephenol). They can be used alone or in combination.

Color developers generally consist of an alkaline aqueous solution containing five color developing agents. The color developing agent is a known primary aromatic amine developer, such as phenylene diamines (e.g., guamino-N, N-diethylaniline, 3-methyl-Hiro-
Amino-N, N-diethylaniline, ≠-amino-N-
Ethyl-N-β-hydroxyethylaniline-3-methyl-≠-amino-N-ethyl-N-β-hydroxyethylaniline-3-methyl-μmamino-N-cy-ruN-β-methanesulfamide ethylaniline .

μm amino-3-methyl-N-ethyl-N-β-methoxyethylaniline, etc.) can be used.

In addition, "Photographic Processing Chemistry" by F. A. Meson, published by Focal Press (1946), pp. 22t-22, U.S. Patent No. 1, 0/! No., same, 2. ! Octopus, 36 Hiro, Tokukai Sho≠r
-tμ933 and the like may be used.

The developer may also contain pH buffering agents such as alkali metal sulfites, carbonates, borates, and phosphates; development inhibitors or antifoggants such as bromides, iodides, and organic antifoggants. can be included. Also, if necessary, a water softener, a hydroxylamine preservative, and benzyl alcohol.

Organic solvents such as diethylene glycol - polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, fogging agents such as sodium boron hydride - l-phenyl-3
- Auxiliary developers, tackifying agents such as pyrazolidones - Polycarboxylic acid chelating agents as described in US Patent μ, 013°723.

It may also contain an antioxidant as described in OLSlu, No. 622.9!0.

When color photographic processing is performed, the photographic light-sensitive material after one color development is usually bleached. The bleaching treatment may be carried out simultaneously with the fixing treatment or may be carried out separately. As a bleaching agent - for example iron (■).

Compounds of polyvalent metals such as cobalt (I[I+, chromium (VI), copper (Ill), peracids, quinones, nitroso compounds, etc. are used. For example, ferricyanide, dichromate, iron C) or Kobal) rill's organic complex salt 1
For example, ethylenediaminetetraacetic acid, nitrilotriacetic acid-1
, 3-diamino-coproch-nortetraacetic acid, or complex salts of organic acids such as citric acid, tartaric acid, and malic acid; persulfate-permanganate; nitrosophenol, and the like can be used. Among these, potassium ferricyanide, iron ethylenediaminenishacetate (
Ill) Sodium and iron ethylenediaminetetraacetate (T
fi) Ammonium is particularly useful. Iron ethylenediaminetetraacetate ((IN complex salt has -
Also useful in bath bleach-fix solutions.

For bleaching or bleach-fixing solutions, US Pat.
No. 0, same 3. ko4t1. Ri Otsu wo-Special Public Showa 4Lj-rr
Bleaching accelerators described in JP-A No. 06, JP-Ko-Ko-UT-RR-3A, etc., JP-A-Ko! In addition to the thiol compounds described in J-6JL-732, various other additives may also be added. Further, after the bleaching or bleaching/fixing treatment, a water washing treatment or a stabilizing bath treatment may be sufficient.

The present invention will be further explained below with reference to Examples, but the present invention is not limited thereto.

Example 1 Dissolved KQN H2O1ooocc Bone gelatin 30f NaC71! At Solution■ H2Ox o ocC AgNO32ot Soluti, o H2O2oocc NaC12,3? Solution 'D H2O600cc AgNO3/30f Solution [F] H2Oz o mark Naα 7.32 to 2Irα6 (0,001%) 3. The OCC solution was heated to 700C and the solution [F
] and solution O at the same time over 5 minutes. Thereafter, the solution and solution [F] were added simultaneously over 3θ minutes. After desalting, emulsion A was obtained by adding diphenylthiourea and sulfur sensitization. The emulsion had cubic grains with uniform grain size and an average volume equivalent to a sphere diameter of 0.7 μm. Sensitizing dye (
j, r'-diphenyl, 9. Ethyl-3,37-di(
3-sulfopropyl, oxacarbocyanine sodium #) were added, and a stabilizer (11-hydroxy-4-
methyl-/, j, Ja, 7-chitrazaindene), coating aid C sodium dodecylbenzenesulfonate), hardener (
2,μ-, dichloro-6-hydroxy-5-) riazine sodium salt) and the following coupler were added and coated with a gelatin protective layer.

α The compound of the present invention (11 in JX/o mol per 7 mol of silver halide) was added to Emulsion A, and the same additives as in Sample were added to obtain Sample 1. Before the emulsion was sulfur sensitized with diphenylthiourea. Emulsion B was prepared by adding the compound of the present invention (11 in an amount of 3×10 mol per mol of silver halide) to obtain Sample 3.

l-phenyl-!, a typical antifoggant in emulsion A!
-mercaptotetrazole per 7 moles of silver halide
xio mol was added to obtain sample 1.

Silver chlorobromide emulsion C was obtained in the same process as emulsion A.

Emulsion C has a silver chloride content of 30 mol, with the remainder being silver bromide, and is in the form of cubes of uniform size. The spherical diameter of the average volume is 0. t was 7 μm. Emulsion C was coated in the same manner to obtain a sample. Each sample was subjected to the following development process and the fog, sensitivity and r values were measured, and the results shown below were obtained.

Development 33°Cjo seconds - 3 minutes 30 seconds Bleach fixing 33°CI minutes 30 seconds Rinse 21r - 33°C 7 minutes 30 seconds C Developer formulation) Color developer diethylenetriaminepentaacetic acid, jNa co, Ofbenzyl alcohol /! d Diethylene glycol 10 Go Na2SO3i, or KBr t,oy Hydroxylamine sulfate J, Of≠-Amino-
3-Methyl-N-ethyl-N-[β-(methanesulfonamido)ethyl]-p-phenyl diamine sulfate! ,02Na2C0
3 (i water salt) 30. Of fluorescent brighteners (stilbene type) 1. Or add water and make the whole amount
/ 000ml (pH 10, ko) (Bleach-fix solution formulation) Ammonium thiosulfate (j≠wt) lyo0ydNa2
SO3/If NH4(Fe((I[)(EDTA)) r
jfEDTA・2Na u?
Add glacial acetic acid r, J/f water and make the total amount tooml (pHj, Hiroshi) (Rinse liquid formulation) EDTA-co-Na-co-H20o, 000rrtl (pH 7,0) Sample 1 (comparative example) Emulsion A ( Sample 2C (invention) Emulsion A (Agα cube) Added compound (1) Sample 3C
Invention) Emulsion B (Compound (1) added before AgQ!cube sulfur sensitization) Sample ≠ (Comparative example) Emulsion A (AgCl!cube) with antifoggant added sample!
(Comparative example) Emulsion C (AgC10, j-Br O, 7 cubes) Sensitivity is expressed as the reciprocal of the exposure that gives a density of fog +/, 0,
Sensitivity ioθ at 3'30'' development of each sample.-
indicates that the concentration is low and sensitivity and γ cannot be determined. As can be seen from the examples, when a compound of the present invention is present, AgQ? It can significantly reduce the smudge characteristic of emulsions.

Furthermore, it not only suppresses the deterioration of development progress and rK that occurs with conventional antifoggants, but also suppresses the development progress and rK.
A very favorable effect can be obtained. It can therefore be seen that high silver chloride emulsions containing the compounds of the present invention are highly preferred as emulsions for rapid processing.

Example J A sample was prepared in the same manner as sample λ in Example/, except that the compound of the present invention + 2L (71, αα-〇〇) was added in place of compound (11), and treated in the same manner as in Example 1. The results are shown in the table below.

However, the relative sensitivity was the same as in Example 1, and each sample was
The sensitivity of !O" is expressed by setting the value at the time of /j"development as 100.

As is clear from the table, the addition of the compound of the present invention suppressed fog and at the same time produced favorable results in development progress and rK.

Preferred embodiments of the invention are as follows.

1. A light-sensitive material according to claim 1, wherein the compound represented by formula (I) is added to the emulsion after silver halide grain formation and before coating.

2. A photosensitive material according to the claims, characterized in that at least 0 mol % of the silver halide is chloride.

3. A light-sensitive material according to the claims, characterized in that at least t mol % of the silver halide is chloride.

≠, bromine or iodine is present in the vicinity of the surface of the silver halide grains, the light-sensitive material according to the claims.

! , a photosensitive material according to the claims, characterized in that it is spectrally sensitized with a methine dye.

Claims (1)

[Scope of Claims] In a silver halide photographic material having at least one silver halide emulsion layer on a support, at least 50 mol% of the silver halide in the silver halide emulsion layer is chloride. and the following general formula (
A silver halide photographic material containing a compound represented by I). General formula (I) ▲There are numerical formulas, chemical formulas, tables, etc.▼ In the formula, Z^1 represents the atomic group necessary to form a saturated or unsaturated heterocycle with the sulfur atom, and this heterocycle is a substituent. It may have.