JPH02108037A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To increase the sensitivity to a low illuminance exposing and to obtain hard images without impairing photographic characteristics by incorporating specific compd. into an emulsion layer. CONSTITUTION:The average iodine content of a silver halide is >=6mol% and the oxidation potential of spectral sensitization dye is +0.98 (VvsSCE) or the value baser than this value; in addition, the compds. expressed by the formula I or the formula II are incorporated into the emulsion layer or other hydrophilic colloidal layers. In the formula I, X, Y denote -H, -OH, -Cl-, -OM (M is an alkaline metal ion), amino group, carboxyl group, sulfone group, sulfonated amino group, sulfonated carbonyl group, carboxyamino group, alkyl group, carboxyalkyl group, sulfonated alkyl group, hydroxyalkyl group, alkyl ether group, alkylthioether group. The sensitivity in long-time exposing under low illumination is improved in this way and the hard-contrast image is obtd.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a silver halide photographic light-sensitive material, and is capable of increasing sensitivity during long exposure, particularly under low illumination, and obtaining high-contrast images. This invention relates to a silver halide photographic material characterized by:

(Prior art) It has previously been found that with silver halide grains, sensitivity decreases when exposed to long periods of time under low illuminance or short exposures under high illuminance, even if the exposure amount is equal, compared to exposure under appropriate illuminance. better known. Generally, the former is called a low-light failure, and the latter is called a high-light failure. Moreover, this low illuminance failure is often accompanied by a softening of the contrast.

In fact, exposure at low illuminance is carried out in astronomical photography, autoradiography, etc., but sufficient image quality cannot be obtained due to decreased sensitivity due to low illuminance failure.

The cause of low-light failure is currently that the unstable latent image precursor has a low density of photogenerated electrons, and before it becomes a stable latent image, it thermally decomposes, recombines with holes, and degenerates. This is interpreted as causing inefficiency.

Furthermore, a sensitizing dye that captures holes is known as a medium for this hole recombination. It is explained that the holes captured by the dye (dye holes) move between the aggregated dyes with relatively high mobility and bleach the latent image precursor (Tadaaki Tan1゜Photograph).
hic 5science and engineering
ng, Vol, 26, 5, p213 (1982
). It is known that the ability of this dye to capture holes corresponds to the oxidation potential of the dye (Tadaak
i Tan1. J.

Electrochem, Soc, +120.25
4. (1973)).

As a method to improve low-light failure, there is knowledge of increasing the after-ripening time to make the photosensitive nuclei tend to disperse, or by making iridium present during silver halide growth. There was a decrease in sensitivity during exposure, and it could not be said to be sufficient. Hydrogen sensitization is known as a method to effectively improve low-light failure without adversely affecting photographic properties, but this is a method in which the coated sample is held in a hydrogen atmosphere. This is difficult to achieve with boat fishing.

(Objective of the Invention) The object of the present invention is to have a photosensitive silver halide in at least one layer on a support, to have an average normality content of the silver halide grains of 6 mol% or more, and to be oxidized during and after exposure. Potential is +
In light-sensitive silver halide photographic materials that have been spectrally sensitized with a sensitizing dye having a value less than 0.98 (V vs SCE), the sensitivity to low-light exposure can be increased without impairing the photographic properties at high or appropriate illuminance. The object of the present invention is to provide a silver halide photographic material having high contrast images.

(Disclosure of the Invention) As a result of intensive research, the present inventor has discovered that at least one
In a photographic light-sensitive material having a silver halide emulsion layer spectrally sensitized by a spectral sensitizing dye in the layer, the average iodine content of the silver halide is 6 mol% or more, and the oxidation potential of the spectral sensitizing dye is is +0°98 (VvsS CE) or a value less than that, and at least one compound selected from the compounds represented by the following general formulas [A] and CB) is contained in the emulsion layer or other hydrophilic colloid layer. It has been found that the above object can be achieved by a silver halide photographic material characterized by containing:

It represents a phonated carbonyl group, a carboxyamino group, an alkyl group, a carboxyalkyl group, a sulfonated alkyl group, a hydroxyalkyl group, an alkyl ether group, or an alkylthioether group (the number of carbon atoms is 4 or less). X
and Y may be the same or different.

(Specific structure of the invention) A specific configuration of the present invention will be explained in detail.

In the compounds represented by the following general formulas [A] and [B], OH Preferred examples of H X,, Y include -H, -OH.

CI! , COOH, CH2COOHl CHs, CH
2CH3, 5OzH, 5CHs, NH2, etc.

X and Y may be the same or different.

Particularly preferred representative compounds among the compounds represented by the general formulas [A] and [B] are listed below.

A-(21 A-(31 A-00) 8-〇〇A-■ 0■ 0■ H B-+11 B-+21 B-(31 A-+41 A-(51 A-(61 B-(51 B) -(61 A -fi+ A -+8+ A -+91 B -(71 B -(81 B -(9) 0■ B -QOI B-(transition) B -Q31 The substituents X, Y and the compound of the present invention are: It is not limited to the above.

These compounds of the present invention may be added to the emulsion layer of the sensitive material or to layers other than the emulsion layer. Also,
It may be added in one or more layers or in a plurality of layers.

The amount added is 3 g or less per log weight of hydrophilic protective colloid such as gelatin in the photosensitive material, but the amount added is preferably 50 to 1 g, particularly preferably 100 to 700 g.

In addition, as stabilizers for the compounds represented by the general formulas A and B of the present invention, sulfites, bisulfites, hydroxyamines,
Ascorbic acid, alkalamine sulfinic acid, etc.
May be added.

The oxidation potential of the sensitizing dye used in the present invention is +0.98 (V
vsSCE) or less.

More preferably a value of +0.91 (VvsSCE) or less and +0.50 (VVSSCE)
Or a sensitizing dye with a higher sensitivity value is better.

The measurement of oxidation potential is described in "Journal of Imaging, Science J.
ingScience), Volume 30, pp. 27-35 (
This was carried out using phase-discriminative second-harmonic AC polarography described in (1986). Details are described below. Acetonitrile (spectral grade) dried in 4A-1/16 molecular sieves was used as the solvent for the sensitizing dye, and normal tetrapropylammonium perchlorate (a special reagent for polarography) was used as the supporting electrolyte.

The sample solution was prepared by dissolving 10-3 to 10-5 mol/1 of the sensitizing dye in acetonitrile containing 0.1 M of supporting electrolyte, and passed through a highly alkaline aqueous solution of pyrogallol and then through calcium chloride before measurement. Oxygen was removed using ultra-high purity argon gas (99,999%) for over 15 minutes. A platinum disk electrode (4 m in diameter) was used as the working electrode, a saturated calomel electrode (SCE) was used as the reference electrode, and platinum was used as the counter electrode. The reference electrode and the sample solution were connected by a Luggin tube filled with acetonitrile containing O and IM supporting electrolytes, and Pycole glass was used for the liquid junction. Measurements were taken at 25° C. with the tip of the Luggin tube and the tip of the platinum disk electrode separated by 811 points from the four dragons.

The sensitizing dye used in the present invention is preferably represented by the following general formulas (I), (II) and (III).

General formula (1) In the formula, Q1, Q2, Q3, Q4 and Q5 represent an atomic group necessary to form a 5- or 6-membered nitrogen-containing ring. D.
and ' represents an atomic group necessary to form an acidic nucleus, and may be acyclic or cyclic. Wl represents an atomic group necessary to form a 5- or 6-membered heterocycle. R8 represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a heterocyclic group. L.I.
%L2, R3, R4, R5, R6, Lfu, Le
, R9, L+o, L+1, L12, L12, L12,
LIS, L12, Ll? , L 111% L 19, L
zo, R21 and R22 represent an optionally substituted methine group. R1, R2, R3, R4 and R6 represent substituted or unsubstituted alkyl groups. l, and 1
2 is an integer from 1 to 3. 7!3 and 7!4 are θ~3
a n+ Sn2 , ns , na , which is an integer of
ns and nb are 0 or 1. M represents a charge-balancing counterion, and m is a number greater than or equal to 0 necessary to balance the charges.

General formulas (1), (II) and (I[l) will be explained in detail below.

The nucleus formed by Ql, Q2, Q3, Q4 and Q includes a thiazole nucleus (e.g. thiazole, 4-methyldeazole, 4-phenylthiazole, 4,5-dimethylthiazole, 4,5 diphenylthiazole, etc.)
, benzothiazole core (e.g., hendithiazole, 4
-Chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 5-nitrobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 6-bromo benzothiazole,
5-iodobenzothiazole, 5-phenylbenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-ethoxybenzothiazole, 5
-Ethoxycarbonylbenzothiazole, 5-carboxybenzothiazole, 5-phenethylbenzothiazole, 5-fluorobenzothiazole, 5-chloro-6-methylbenzothiazole, 5,6-dimethylbenzothiazole, 5,6-simethoxybenzothiazole , 5-hydroxy-6-methylbenzothiazole, tetrahydrobenzothiazole, 4-phenylbenzothiazole, etc.)
, naphthothiazole nucleus (e.g. Nando(2,1-d)
Thiazole, naphtho(1,2-d)thiazole, naphtho(2,3-d)thiazole, 5-methoxynaphtho(1,
2-d) Thiazole, 7-nitronaphtho (2,1-d)
) thiazole, 8-methoxynaphtho(2,1-d)thiazole, 5-methoxynaphtho(2,3-d)thiazole, etc.), thiazoline core (e.g., thiazoline, 4-methoxynaphtho(2,3-d)thiazole, etc.)
-methylthiazoline, 4-nitrothiazoline, etc.), oxazole nucleus (oxazole nucleus (e.g., oxazole, 4-methyloxazole, 4-nitrooxazole,
5-methyloxazole, 4-phenyloxazole,
4,5-diphenyloxazole, 4ethyloxazole, etc.), benzoxazole nuclei (e.g., benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5-bromobenzoxazole,
5-fluorobenzoxazole, 5-phenylbenzoxazole, 5-methoxybenzoxazole, 5-
Nitrobenzoxazole, 5-trifluoromethylbenzoxazole, 5-hydroxybenzoxazole, 5-carboxybenzoxazole, 6-methylbenzoxazole, 6-chlorobenzoxazole, 6-
2I-lobenzoxazole, 6-methoxybenzoxazole, 6-hydroxybenzoxazole, 5.6-
dimethylbenzoxazole, 4,6-dimethylhenzoxazole, 5-ethoxybenzoxazole, etc.)
, naphthothiazole nucleus (e.g. naph) (2,1-d
) oxazole, natu[1,2d]oxazole, naphtho(2,3-d)oxazole, 5-nitronaphtho(
2,1-d) oxazole), etc.), oxazoline core (
For example, 4゜4-dimethyloxazoline, etc.), selenazole nucleus (e.g., 4-methylselenazole, 4-nitroselenazole, 4-phenylselenazole, etc.), benzoselenazole nucleus (e.g., benzoselenazole, 5-chlorobenzoselenazole, 5-nitrobenzoselenazole, 5-methoxybenzoselenazole, 5-hydroxybenzoselenazole, 6-nitrobenzoselenazole, 5-chloro-6-nitrobenzoselenazole, 5.6-chlorobenzoselenazole methylbenzoselenazole, etc.)
, naphthoselenazole core (e.g., naphtho[2,1d]
selenazole, naphtho(1,2-d) selenazole, etc.), selenazoline core (e.g. selenazoline, 4
- methylselenazoline, etc.), telllazole core (e.g., tellurazole, 4-methylthiazoline, 4-phenyltelllazole, etc.), penzotelllazole core (e.g., Eva, penzotelllazole, 5-chloropenzotellazole, etc.) sol, 5-methylbenzotellurazole, 5.
6-dimethylbenzotelllazole, 6-medoxybenzotelllazole, etc.), naphthotellazole core (e.g.,
naphtho(2,1-d)tellazole, naphtho(1,2-
d) telllazoline etc.), tellazoline core (e.g. telllazoline, 4-methylselenazoline etc.), 3
．． 3-dialkylindolenine core (e.g., 3,3-dimethylindolenine, 3,3-diethylindolenine,
3.3-dimethyl-5-cyanoindolenine, 3゜3-
Dimethyl-6-nitroindolenine, 3,3 dimethyl-
5-nitroindolenine, 3,3 dimethyl-5-methoxyindolenine, 3,3゜5-trimethylindolenine, 3,3,5-dimethyl-5-chloroindolenine, etc.), imidazole nucleus (imidazole nucleus (e.g. , 1-alkylimidazole, l-alkyl-4-phenylimidazole, etc.), henchimidazole core (e.g., 1-
Alkylhenshiimidazole, 1-alkyl-5-chlorobenzimidazole, 1-alkyl-5,6-dichlorobenzimidazole, 1-alkyl-5-methoxybenzimidazole, 1-alkyl-5-cyanobenzimidazole, ■ Alkyl-5-fluorobenzo imitasol, 1-alkyl-5-trifluoromethylbenzimidazole, 1-alkyl-6-chloro-5-cyanobenzimitazole, 1-alkyl-6-chloro-5-trifluoromethylbenzimidazole, 1-allyl -5,6-
Dichlorobenzimidazole, 1-allyl-5-chlorobenzimidazole, 1-aryl-imidazole, 1-
Arylbenzimidazole, ■-aryl-5-chlorobenzimidazole, 1-aryl-5,6-dichlorobenzimidazole, l-aryl-5-methoxybenzimidazole, 1-aryl-5-cyanohencyimidazole, etc.), naphthimidazole nucleus (For example, 2
-alkylnaphtho(1,1-d)imidazole, l-arylnaphtho(1,1-d)imidazole, etc.), the aforementioned alkyl groups having 1 to 8 carbon atoms, such as methyl, ethyl, propyl, isopropyl , unsubstituted alkyl groups such as butyl, and hydroxyalkyl groups (e.g., 2-
hydroxyethyl, 3-hydroxypropyl, etc.) are preferred. Particularly preferred are methyl group and ethyl group. The aforementioned aryl groups represent phenyl, halogen (eg, chloro) substituted phenyl, alkyl (eg, methyl) substituted phenyl, alkoxy (eg, methoxy) M-substituted phenyl, and the like. ), pyridine core (e.g. 2-pyridine, 4-
Pyridine, 5-methyl-2-pyridine, 3-methyl-4
-pyridine, etc.), quinoline nucleus (e.g.
2-quinoline, 3-methyl-2-quinoline, 5-ethyl-
2-quinoline, 6-methyl-2-quinoline, 6-nitro-2-quinoline, 8-fluoro2-quinoline, 6-medoxy-2-quinoline, 6-hydroxy-2-quinoline, 8
-Chloro-2-quinoline, 4-quinoline, 6-nitoxy-4-quinoline, 6-nitro-4-quinoline, 8-chloro-4-quinoline, 8-fluoro-4-quinoline, 8-methyl-4-quinoline, 8- Methoxy-4-quinoline, 6-methyl-4-quinoline, 6-medoxy-4-quinoline, 6
-chloro-4-quinoline, etc.), isoquinoline nuclei (e.g., 6-nitro-1-isoquinoline, 3,4-dihydro-
1-isoquinoline, 6-nitro-3-isoquinoline, etc.), imidazo(4,5-b)quinoxaline core (e.g., ■, 3-diethylimidazo[4,5b]quinoxaline, 6-chloro-1,3- Diallylimidazo (4,5
-b) quinoxaline, etc.), oxadiazole nucleus, thiadiazole nucleus, tetrazole nucleus, pyrimidine nucleus, etc.

More preferred is a benzothiazole nucleus.

D,, DI' represent an atomic group necessary to form an acidic nucleus, and can take the form of an acidic nucleus of any general merocyanine dye. In a preferred form, Dl is a cyano, sulfo or carbonyl group, and D+' represents the remaining atoms necessary to form the acidic nucleus.

When the acidic nucleus is acyclic, i.e. Dl and D+'
When is an independent group, the terminus of the methine linkage is a group such as malononitrile, alkylsulfonylacetonitrile, cyanomethylbenzofuranyl ketone or cyanomethylphenyl ketone.

D, , D,' together form a 5- or 6-membered heterocycle consisting of carbon, nitrogen, and chalcogen (typically oxygen, sulfur, selenium, and tellurium) atoms.

Preferably DI, D,' together complete the next nucleus.

2-pyrazolin-5-one, pyrazolidine-3°5-dione, imidacillin-5-one, hydantoin, 2- or 4-thiohydantoin, 2-iminooxazolidine-
4-one, 2-oxazolin-5-one, 2-thioxazolidine-2,4-dione, isoxazolin-5-one, 2-thiazolin-4-one, thiazolidin-4-one, thiazolidine-2,4-dione, rhodanine, thiazolidine-2,4-dithione, isorhodanine, indan-1,3-dione, thiophen-3-one, thiophen-3-one-1,1-dioxide, indolin-2-one, indolin-3-one, indublin-3-on,
2-oxoindasilinium, 3-oxoindasilinium, 5,7 dioxo 6,7-cyhydrothiazolo[3
, 2a] pyrimidine, cyclohexane-1,3-dione, 3,4-dihydroisoquinolin-4-one, 1.3-
Nuclei of dioxane-4,6-dione, barbylic acid, 2-thiobarbylic acid, chroman-2°4-dione, indacillin-2-one, or pyrido(1,2-a)pyrimidine-1,3-dione.

More preferably, 1,3-dialkylbarbylic acid, 1,3-dialkyl-2-thiobarbylic acid, 3-
It is an alkylrhodanine (the alkyl group is preferably an unsubstituted alkyl group).

The substituent bonded to the nitrogen atom contained in the nucleus is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, preferably 1 to 7 carbon atoms, particularly preferably 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, Isopropyl group, butyl group, isobutyl group,
hexyl group, octyl group, dodecyl group, octadecyl group, etc.), substituted alkyl groups (e.g. aral: tolu group (e.g. benzyl group, 2-phenylethyl group, etc.), hydroxyalkyl group (e.g. 2-hydroxyethyl group, 3-hydroxy propyl group, etc.), carboxyalkyl group (e.g., 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, carboxymethyl group, etc.), alkoxyalkyl group (e.g., 2-methoxyethyl group, 2-(2 methoxyethoxy)ethyl group, etc.), sulfoalkyl group (e.g. 2-sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, 2-[3-sulfopropoxy]ethyl group, 2-hydroxy- 3-sulfopropyl group, 3-sulfopropoxyethoxyethyl group, etc.), sulfbutoalkyl group (e.g., 3-sulfa-1-propyl group, 4-sulfatobutyl group, etc.), heterocyclic-substituted alkyl group (e.g., 2-( (pyrrolidin-2one-1-yl)ethyl group, tetrahydrofurfuryl group, 2-morpholinoethyl group, etc.), 2-acetoxyethyl group, carbomethoxymethyl group, 2-methanesulfonylaminoethyl group, etc.), allyl group, aryl group (e.g., phenyl group, 2-naphthyl group, etc.), substituted aryl group (e.g., 4-carboxyphenyl group, 4-sulfophenyl group, 3-chlorophenyl group, 3-methylphenyl group, etc.), heterocyclic group (e.g., 2-naphthyl group, etc.), -pyridyl group, 2-thiazolyl group, etc.) are preferred.

In addition, a 5- or 6-membered heterocycle formed by W,
It is a cyclic heterocycle represented by Dl or D1' from which an oxo group or a thioxo group at an appropriate position is removed.

R6 is preferably the same as the substituent described above as a substituent bonded to the nitrogen atom contained in the nucleus of the cyclic heterocycle represented by D+ or D+'.

L,, R2, R4, R4, Ll, R6, R7, Le,
Lq, L+o, Lll, Ll2, Lll, Ll4, L
l5, Ll6, L+? , Lll1% Ll9, R2゜,
R21 and L2□ are methine group (substituted or unsubstituted alkyl group (e.g. methyl group, ethyl group, etc.), substituted or unsubstituted aryl group (e.g. phenyl group, etc.)
or halogen atoms (e.g. chlorine atom, bromine atom, etc.)
may be replaced with . ), and may form a ring with another methine group, or may form a ring with an auxochrome.

RI, R2, R3, R4 and R2 can take the form of quaternizing substituents of the basic core of any cyanine dye.

For example, preferably an unsubstituted alkyl group having 18 or fewer carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an octyl group, a decyl group, a pyridyl group, an octadecyl group, etc.) or a substituted alkyl group (such as a substituted Examples of the group include a carboxyl group, a sulfo group, a cyano group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), a hydroxy group, an alkoxycarbonyl group having 8 or less carbon atoms (for example, a methoxycarbonyl group, an ethoxycarbonyl group) group, phenoxycarbonyl group, benzyloxycarbonyl group, etc.), alkoxy group having 8 or less carbon atoms, (
For example, methoxy group, ethoxy group, benzyloxy group, phenethyloxy group, etc.), monocyclic aryloxy group having 10 or less carbon atoms (for example, phenoxy group, p-tolyloxy group, etc.), acyloxy group having 3 or less carbon atoms (for example, acetyloxy group, propionyloxy group, etc.), acyl group having 8 or less carbon atoms (e.g. acetyl group, propionyl group, benzoyl group, mesyl group, etc.), carbamoyl group (e.g. carbamoyl group, N,N-dimethylcarbamoyl group, morpholinocarbonyl group) group, piperidinocarbonyl group, etc.), sulfamoyl group (e.g. sulfamoyl group, N
, N-dimethylsulfamoyl group, morpholinosulfonyl group, piperidinosulfonyl group, etc.), aryl groups having 10 or less carbon atoms (e.g. phenyl group, 4-chlorophenyl group, 4-methylphenyl group, α-naphthyl group, etc.) ) and the like, and an alkyl group having 18 or less carbon atoms is preferable.

) can be mentioned.

M is included in the formula to indicate the presence or absence of a negative ion or anion when necessary to neutralize the ionic charge of the dye. Whether a dye is cationic, anionic, or has a net ionic charge depends on its auxochromes and substituents. Counterions can be easily exchanged after the dye is manufactured.

Typical cations are ammonium ions and alkali metal ions, while anions may specifically be either inorganic or organic anions, such as halogen anions (e.g. fluoride, chloride,
bromide ion, iodide ion, etc.), substituted arylsulfonate ion (e.g. p-toluenesulfonate ion, p-toluenesulfonate ion, etc.).
-chlorobenzenesulfonate ion, etc.), aryldisulfonate ion (e.g. 1,3-benzenedisulfonate ion, 1,5-naphthalenedisulfonate ion, 2
．． (6-naphthalenedisulfonate ion, etc.), alkyl sulfate ion (e.g. methyl sulfate ion, etc.), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, picrate ion, acetate ion, trifluoromethanesulfonate ion Examples include.

Preferably it is an iodine ion.

Among the spectral sensitizing dyes represented by general formulas (1), (II) and (II[), a more preferable spectral sensitizing dye is represented by the following general formula (IV).

General formula (IV) In the Nagi formula, 21 is an oxygen atom, a sulfur atom, a selenium atom, or R7 or a nitrogen atom (-N-1R7 is a general formula (1), (II)
and (1) R+, Rz, R3, R4 and R3
(synonymous with). More preferred is a sulfur atom. Z2 represents an oxygen atom, a sulfur atom or a selenium atom, preferably a sulfur atom.

LZI, R24 and R25 are general formula (I) glue 8, R
4 and R5. β is an integer from 1 to 3.

R7 and R6 have the same meanings as R3 and R2 in general formula (I).

M and ' have the same meaning as MII in general formula (1).

Two ■3, v2, v3, V4, ■1, V6, ■, and v8
are hydrogen atoms and halogen atoms (for example,
chlorine, fluorine, bromine), unsubstituted alkyl groups with 10 or less carbon atoms (e.g., methyl, ethyl), more preferably substituted alkyl groups with 18 or less carbon atoms (e.g., Benzoyl, α-
naphthylmethyl, 2-phenylethyl, trifluoromethyl), an acyl group more preferably having 10 carbon atoms or less (e.g. acetyl, benzoyl, mesyl), an acyloxy group more preferably having 10 carbon atoms or less (e.g. acetyloxy group, etc.), an alkoxycarbonyl group preferably having 10 or less carbon atoms (e.g., methoxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl), a substituted or non-substituted carbamoyl group (e.g., carbamoyl,
N,N-dimethylcarbamoyl, morpholinocarbonyl, piperidinocarbonyl), carboxy group, cyano group,
An acylamino group having 8 or less carbon atoms (e.g., acetylamino) is more preferable than a hydroxy group, an amino group, or an acylamino group, and an alkoxy group having 10 or less carbon atoms (e.g., methoxy, ethoxy, benzyloxy), an alkylthio group is more preferable than an alkoxy group. (e.g., ethylthio), alkylsulfonyl groups (e.g., methylsulfonyl, etc.)
, sulfonic acid group, aryloxy (eg, phenoxy), aryl group (eg, phenyl, tolyl). Moreover, two bonded to adjacent carbon atoms in (1) and ~V8 may be bonded to each other to form a condensed ring.

For example, fused rings include benzene rings and heterocycles (eg, pyrrole, thiophene, furan, pyridine, imidazole, triazole, thiazole).

General formulas (1), (II), ([1) and (I) of the present invention
Specific examples of the dye represented by V) are shown below.

However, it is not limited to these.

Oxidation potential (Box) is measured using counter ions (Mka and M
1') was exchanged with p-toluenesulfonate ion, perchlorate ion, pyridinium ion or tetraethylammonium ion.

■ Et SO,I SQ, -Na' ■ Et 0S- 3O3-(CH3CI+2)3N''ll■ Et ■ Et Et ■ Et Et de (CI+2)4I3 The above general formulas (1), (II), (III) or G (r
In order to incorporate the sensitizing dyes represented by V) into the silver 10-genide emulsion of the present invention, they may be directly dispersed in the emulsion, or they may be dispersed in water, methanol, ethanol, propatool, methyl Cellosol, 22.3.3-tetrafluoroprono may be dissolved in a solvent such as alcohol alone or in a mixed solvent and added to the emulsion. In addition, the special public
No. 4-23,389, Japanese Patent Publication No. 44-27.555, Japanese Patent Publication No. 57-22089, etc., an aqueous solution is prepared by coexisting an acid or a base, or U.S. Patent No. 3,822,135,
As described in US Pat. No. 4,006,025, an aqueous solution or colloidal dispersion may be added to the emulsion in the presence of a surfactant. In addition, after dissolving fluoro■ ■ Et TS Et Et r Et ■ e φ Et ■ Et in a substantially water-immiscible solvent such as enoxyethanol, the dispersion in water or a hydrophilic colloid is added to the emulsion. It's okay. As described in JP-A-53102.733 and JP-A-58-105,141, it may be directly dispersed in a hydrophilic colloid, and the dispersion may be added to the emulsion.

It may be added to the emulsion at any stage of emulsion preparation known to be useful. Chemical sensitization is most commonly carried out after completion of chemical sensitization but before application, but as described in U.S. Pat. The spectral sensitization can be carried out at the same time as the chemical sensitization by adding the agent at the same time as the silver halide grains, or it can be carried out before the chemical sensitization as described in JP-A No. 58113.928. It is also possible to start spectral sensitization by adding it before the completion of precipitation formation. Furthermore, U.S. Pat. No. 4,225.
It is also possible to add these said compounds separately as taught in No. 666, i.e. some of these compounds can be added before chemical sensitization and the rest after chemical sensitization. and at any time during silver halide grain formation, including the method taught in U.S. Pat. No. 4,183,756.

The amount of the compound represented by formula (I), (II), (Ill) or (IV) added is generally about 4×10 per mole of silver halide of the silver halide emulsion in the layer containing the high silver chloride emulsion. -6 to 8 x 10-'' mol, preferably 1 x 10 to 6 to 1 x 10-3 mol,
More preferably, it is 5XIO-5 to 5XIO-'mol.

As the silver halide in the photosensitive silver halide emulsion used in the present invention, silver iodobromide and silver chloroiodobromide can be used, but silver iodobromide is preferably used. Here, the content of silver iodide is preferably in the range of 6 mol% or more, preferably 30 mol% or less, particularly 20 mol% or less. The distribution of iodine in the silver iodobromide grains may be uniform or may be different between the inside and the surface. The average particle size is preferably 0.3 μm. In particular, it is preferably 0.5 to 2.0 μm. The particle size distribution may be narrow or wide.

The silver halide grains in the emulsion may have regular crystal shapes such as cubic, octahedral, tetradecahedral, rhombic dodecahedral, etc., or may have irregular crystal shapes such as spherical, plate-like, potato-like, etc. It may consist of a mixture of particles of various crystalline forms, which may have irregular crystalline forms or may have composite forms of these crystalline forms. Further, tabular grains having a grain size of 5 times or more the grain thickness may be used (for details, refer to RESEARCH DISCLO
3URE Volume 225 Item 225341), 20~
p, 5B, January issue, 1983, and JP-A-58-12
No. 7921 and No. 58-113926.

Among tabular silver halide grains, monodisperse hexagonal tabular grains are one of useful grains.

The details of the structure and manufacturing method of the monodispersed hexagonal tabular grains used in the present invention are as described in Japanese Patent Application No. 61-299155, but briefly, the emulsion is composed of a dispersion medium and silver halide grains. A silver emulsion in which 70% or more of the total projected area of the silver halide grains has a ratio of the length of the side with the maximum length to the length of the side with the minimum length of 2 or less. It is occupied by tabular silver halide grains that are hexagonal and have two parallel surfaces as outer surfaces, and furthermore, the coefficient of variation of the grain size distribution of the hexagonal tabular silver halide grains [the circle of its projected area] It has a monodispersity of 20% or less (the value obtained by dividing the variation (standard deviation) of the particle size expressed by the converted diameter by the average particle size). Although the crystal structure may be --like, it is preferable that the inside and outside have different halogen compositions, and may have a layered structure. Further, it is preferable that the particles contain reduction-sensitized silver nuclei.

The silver halide grains can be produced through nucleation-Ostwald ripening and grain growth,
The details are as described in Japanese Patent Application No. 61-299155.

Further, the silver halide grains used in the present invention may be used by forming a core/shell type shallow latent type emulsion with the hexagonal tabular grain as a core. In this case, regarding the chemical sensitization method of the core, the method of attaching the shell, and the development with a developer containing a silver halide solvent, Japanese Patent Application Laid-Open No. 59-1335
No. 42, British Patent No. 145,816 may be referred to.

The thickness of the shell in this case is preferably 1 to 100 lattices, preferably 5 to 50 lattices.

The hexagonal tabular grains used in the present invention may have dislocation lines inside. The presence or absence of dislocation lines and their number can be determined by observing with a low temperature (liquid He temperature) transmission electron microscope.

Hexagonal tabular grains containing dislocation lines are formed by adding iodide salt during the crystal growth period of the hexagonal tabular grains or using the hexagonal tabular grains as seed crystals and adding iodide salt during a certain period of the crystal growth period when the crystals are further grown. can do. In this case, a certain period refers to the entire crystal growth period from an instant (approximately 1/2 second). The rate of addition of the iodide salt is such that the difference between the normal content of silver iodobromide deposited by the addition and the normal content of silver iodobromide of the substrate is 5 mol % or more.

Among the above-mentioned silver halide grains, irregular tabular grains and hexagonal tabular grains having high sensitivity are preferably used.

In the present invention, the photosensitive silver halide emulsion may be a mixture of two or more types of silver halide emulsions. The emulsions to be mixed may differ in grain size, halogen composition, sensitivity, etc., and a substantially non-photosensitive emulsion (
(The surface or interior may or may not be covered) may be used in combination, or may be separated into separate layers (for details, see U.S. Pat. No. 2,996,382, No. 3, No.
97.9 (described in No. 17, etc.) 0 For example, a spherical or potato-shaped photosensitive emulsion and a photosensitive silver halide emulsion consisting of tabular grains with a grain size of 5 times or more than the grain thickness are placed in the same layer or It may be used in different layers as described in JP-A-58-127921. When used in different layers, the photosensitive silver halide emulsion consisting of tabular grains may be located on the side closer to the support or, conversely, on the side farther away.

The photographic emulsion used in the present invention is P, Glafkide.
CI+emie eL Ph1sique l”h
oLographique (Paul MonLe1
Publishing, 1967), G, F, Duffin, Ph.
otographjcEmulsion Chemis
try (the Focal Press, 196
6), Making and Coting Photography by V, L, and Zelikman eL al.
phic mulsion (The Focal
Published by Press, 1964) Japanese Patent Publication No. 511-12792
It can be prepared using the methods described in No. 1 and No. 5B-113926. That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt and soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. .

A method in which silver halide grains are formed in an excess of silver ions (so-called back mixing method) can also be used. As one type of simultaneous mixing method, a method in which PAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondrald double jet method can also be used. According to this method, a silver halide emulsion consisting of silver halide grains having a regular crystal shape and a nearly uniform grain size can be easily changed.

Even if the crystal structure of silver halide grains is similar to the inside, there are also grains with a layered structure with different inside and outside, British Patent No. 635,841, US Patent No. 3,622,3
It may be of the so-called conversion type as described in No. 18, or silver halides of different compositions may be bonded by epitaxial bonding, for example silver rhodan, silver oxide, silver halide. It may be bonded with a compound other than the silver compound or with a compound other than the silver compound. Cadmium salt, zinc salt, lead salt, thallium salt, salt, iridium salt or its complex salt,
A rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present together.

Further, during grain formation, grain growth may be controlled by adding a so-called silver halide solvent such as ammonia, thioether compound, thiazolidine-2-thione, tetrasubstituted thiourea, rhodanpotash, rhodanammonium, or amine compound.

The silver halide emulsion used in the present invention may or may not be chemically sensitized. Chemical sensitization methods include sulfur sensitization, reduction sensitization, metal sensitization, and other known methods. The methods described can be used, used alone or in combination.

Among the noble metal sensitization methods, the gold sensitization method is a typical method and uses a gold compound, mainly a gold jIF salt. Precious metals other than all,
For example, it may contain complex salts such as platinum, palladium, and iridium.

As the sulfur sensitizer, in addition to the sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines, etc. can be used.

As a reduction sensitizer, a stout salt, amines, borhamidine sulfinic acid, a silane compound, etc. can be used.

The photographic emulsion used in the present invention may contain certain compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. . That is, thiazoles (e.g. benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, nitroindazoles, benzotriazoles, aminotriazoles, etc.); mercapto compounds (e.g. mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptodeadiazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines, mercaptotriazines, etc.); Thioketo compounds such as; azaindenes (e.g. triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a,7) tetraazaindenes), pentaazaindenes, etc.); benzenethiosulfonic acid A number of compounds known as antifoggants or stabilizers can be added, such as benzenesulfinic acid, benzenesulfonic acid amide, etc.

Specifically, RIESEARCII DISCLO3UR
E Item 17643■ (December 1978 issue P
, 24-P, 25) or in the literature cited therein.

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

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

Useful sensitizing dyes for use in the present invention include, for example, RESEA
RCII DISCLO5LIR[! Item 17
643 1V-A section (December 1978 P, 23), 1teml B 3 lX section (August 1979 P, 43)
7) or in the literature cited.

The sensitizing dye can be used at any stage of the photographic emulsion manufacturing process, or at any stage after manufacturing until immediately before coating. Examples of the former include a silver halide grain formation process, a physical ripening process, and a chemical ripening process.

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, contrast enhancement, 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 ether chains, polyethylene glycol esters, polyethylene glycol alkyl ethers, polyalkylene Nonionic interfaces such as glycolalkylamines or amides, polyethylene oxide adducts of silicone), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Activator; alkyl carboxylate, alkyl sulfonate, alkylbenzene sulfonate, alkylnaphthalene sulfonate, alkyl sulfate, alkyl phosphate, N-acyl-N-alkyl taurine, sulfosuccinate, Anionic surfactants containing acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, such as sulfoalkyl polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphate esters, etc. Amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphates, alkyl betaines, amine oxides and other amphoteric surfactants; Alkylamine salts, aliphatic or aromatic quaternary ammonium salts, pyridinium, imidazo Cationic surfactants such as heterocyclic quaternary ammonium salts such as lithium, and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used. These are "Surfactants and their applications" by Ryohei Oda et al.
(Maki Shoten, 1964), “New Surfactants” by Hiroshi Horiguchi
(Sankyo Shuppan Ti@), 1975) or ``Matsukation Divisions, MC Publishing Company 1985''('
HcCutcl+eon's Deterger+Ls
& Emulsifiers, 1 (McCuLch
eon Divisions, YIGPublisl
+ing Co, 1905) ), Japanese Patent Application Publication No. 1986-
No. 76741, Patent Application No. 1339/1986!1, No. 61-
No. 16056, No. 61-32462, etc.

As antistatic agents, in particular, JP-A-59-74554,
No. 60-80849, Japanese Patent Application No. 60-249021,
Fluorine-containing surfactant or polymer described in JP-A-61-32462, JP-A-60-76742, JP-A-60-00
No. 846, No. 60-80840, No. 60-80113
No. 9, No. 60-76741, No. 5B-208143, Japanese Patent Application No. 61-13390, No. 6l-1 (No. i056, No. 61-3246.2, etc.). Nonionic interface Activator or also JP-A-572045
Conductive polymer or latex (nonionic, anionic,
cationic, amphoteric) can be preferably used. Inorganic antistatic agents include ammonium, alkali metal, alkaline earth metal halogen salts, nitrates, persalt salts, sulfates,
Acetate, phosphate, thiocyanate, etc., as well as conductive tin oxide described in JP-A-57-11 [1242], etc.
Zinc oxide or a composite oxide obtained by doping antimony or the like with these metal oxides can be preferably used.

In the present invention, as a matting agent, a homobomer of polymethyl methacrylate or a polymer of methyl methacrylate and meccrylic acid, an organic compound such as starch, or fine particles of an inorganic compound such as silica, titanium dioxide, sulfuric acid, strontium, or barium can be used. can. The particle size is preferably 1.0 to 10 μm, particularly 2 to 5 μm.

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

Polyols such as trimedylolpropane, bentanediol, butanediol, ethylene glycol, and glycerin can be used as plasticizers in the hydrophilic colloid layer of the photographic material of the present invention. Furthermore, the hydrophilic colloid layer of the photographic material of the present invention preferably contains a polymer latex for the purpose of improving pressure resistance. As the polymer, a homopolymer of an alkyl ester of acrylic acid or a copolymer with acrylic acid, a styrene-butadiene copolymer, or a polymer or copolymer consisting of a monomer having an active methylene group can be preferably used.

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

For example, chromium salts (chromium alum), aldehydes (
formaldehyde, glitaraldehyde, etc.), N-
Methylol compounds (dimethylol urea, etc.), dioxane derivatives, active vinyl compounds (13,5-)lyacryloyl-hexahydro S-) riazine, bis(vinylsulfonyl) methyl ether, N,N'-methylene, bis-
[β-(vinylsulfonyl)propionamide], etc.)
, active halogen compounds (2,4-dichloro-6-hydroxy-8-triazine, etc.), mucohalogen acids, etc. can be used alone or in combination. Among them, JP-A No. 53-41220, No. 5357257, No. 59-1
62546, 60-130E146 and active halides described in U.S. Pat. No. 3,325,287 are preferred.

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

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfate; sodium alginate; polyvinyl alcohol, polyvinyl alcohol partial acetal, and A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of -N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyvinylimidazole, polyvinylpyrazole, and the like.

As the gelatin, in addition to lime-treated gelatin, acid-treated gelatin or enzyme-treated gelatin may be used, and hydrolysates of gelatin may also be used.

In addition to the light-sensitive silver halide emulsion layer, the silver halide photographic material of the present invention may have non-light-sensitive layers such as a surface protective layer, an intermediate layer, and an antihalation layer.

There may be two or more silver halide emulsion layers, and the two or more silver halide emulsion layers may have different sensitivities, gradations, etc.

Further, one or more silver halide emulsion layers or non-photosensitive layers may be provided on both sides of the support.

Cellulose triacetate film is preferred as a support for general sensitive materials, and polyethylene terephthalate film or cellulose triacetate film is preferred as a support for X-ray photography, which may be colored or uncolored for antihalation purposes. is preferable,
In particular, it is preferably colored blue.

In order to improve the adhesion with the hydrophilic colloid layer, the surface of the support is preferably subjected to corona discharge treatment, claw discharge treatment, or ultraviolet irradiation treatment, or is made of styrene-butadiene latex, vinylidene chloride latex, etc. An undercoat layer may be provided, and a gelatin layer may be further provided on top of the undercoat layer. Further, an undercoat layer may be provided using an organic solvent containing a polyethylene swelling agent and gelatin. These undercoat layers can be surface-treated to further improve their adhesion to the hydrophilic colloid layer.

For photographic processing of the light-sensitive material of the present invention, for example, research
5URE>No. 176, pages 28-30 (RI)-1764
Any of the known methods and known treatment liquids as described in 3) can be applied. This photographic processing may be either photographic processing for forming a recorded image (black and white photographic processing) or photographic processing for forming a dye image (color photographic processing), depending on the purpose. Processing temperature is usually 1
The temperature is selected between 8°C and 50'c, but temperatures below 18°C or above 50'c may also be used.

For example, developers used in black-and-white photographic processing can include known developing agents.

As developing agents, dihydroxyhenzenes (e.g. hydroquinone), 3-pyrazolidones (e.g. 1-
phenyl-3-pyrazolidone), aminophenols (
For example, N-methyl-p-aminophenol) can be used alone or in combination. The photographic processing of the light-sensitive material of the present invention can also be carried out using a developer containing imidazoles as a silver halide solvent as described in JP-A-57-78535. Also, JP-A No. 51137
It can be processed with a developer containing a silver halide solvent and an additive such as imidazole or triazole as described in No. 643. The developing solution generally contains other known preservatives, alkaline agents, pH buffering agents, antifoggants, etc., and, if necessary, solubilizing agents, color toners, development accelerators, surfactants, antifoaming agents, etc. Water softeners, hardening agents (eg glutaraldehyde), viscosity imparting agents, etc. may also be included.

As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to periosulfate and thiocyanate, 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 present invention will be explained in more detail with reference to Examples below.

Example 1 (Two 1) In a container containing 25 g of potassium bromide, 8 g of potassium iodide, 9 cc of 2N potassium thiocyanate, and 24 g of gelatin in 1 p of halogen water, 4 g of an aqueous silver nitrate solution was added using the usual ammonia method. An aqueous potassium iodide solution containing potassium iodide was added using a double jet method to obtain an average particle size of 1.0 μn.
A silver iodobromide emulsion having a relatively amorphous thick plate shape with a legal content of 8 mol % was prepared from No.
After addition of molar Ag, chemical sensitization was carried out using sodium thiosulfate and chloroauric acid to obtain a photosensitive silver iodobromide emulsion [A] having a pAg of 8.6 and a pH of 6.4.

Emulsion [B] was prepared in the same manner as emulsion [A], except that the chemical sensitization time was 1.5 times longer than that of emulsion [A]. Further, emulsion [A] was prepared in the same manner as emulsion [A], except that 31rCρ6 was present in the emulsion potassium solution, and emulsion (C
) was obtained. The amount of Ir added to emulsion (C) is 10-8 mol 1
It was molar Ag.

1) Preparation: The emulsion coating surface is undercoated in advance, and the back side is coated with 0 (-CH
,C11□0+5■ (m+n=32)10w/n? On a triacetyl cellulose support coated with 2C 1060 mg/rtr diacetyl cellulose 143 .mu./d and silicon oxide 5 .mu./d, the following formulation was coated on the emulsion-coated side to prepare coated samples 1 to 36.

(Emulsion layer) Coated silver amount 3.5g/n? Gelatin amount 1.5g/Ag1g Compound A Listed in Table 1 4-hydroxy-6methyl-13.3a,
7-chitrazaindene 10w/Ag1g, polyethylene oxide 8w/Ag1g, polypotassium p-vinylbenzenesulfonate 20w/Ag1g, the dura coated sample was stored at 25°C and 65% RH for 7 days, then during distillation at 25°C. The film thickness after immersing for 3 minutes is 200±10 of the dry thick film.
%, the solution was adjusted with bis-(vinylsulfonylacetamido)ethane for 8 times.

(Surface protective layer) Gelatin amount 0.8 g/m Polypotassium p-vinylhenzenesulfonate 1/M polymethyl methacrylate fine particles (average size 3μ) 0.13/d Coating samples 1 to 2
1 was stored for 7 days at a temperature and humidity of 25° C. and 65% RH. The film was developed at 20° C. for 7 minutes using developer A exposed using a filter having a wavelength distribution corresponding to that of sunlight, fixed with a fixer solution, washed with water, and dried. The series of steps of development, fixing, washing, and drying are collectively referred to as post-processing. Sensitometry was performed on post-treatment treatments. The results are shown in Table-1.

Developer A Metol 2g Anhydrous Sodium Sulfite 100g Hydroquinone
5g boric acid
Add water to 2g or more to make 11.

(Adjust pH to 8.7) Karimyeonghan Add water to make 11.

5g Fixer A Sodium thiosulfate 240g Anhydrous sodium sulfite 15g 28% acetic acid
48m! Boric acid
7.58 Comparative Compound-1 O1+ Comparative Compound-2 PhenylhyFloginone Comparative Compound-3 Bromohydroquinone As shown in Table-1, the compound of the present invention [A] was added to the emulsion [A] spectrally sensitized with dye 1-10. By adding A], low-light failure could be improved without affecting the sensitivity in proper exposure and high-light exposure. However, emulsion [B] in which the chemical sensitization time was simply increased improved the low-light-intensity failure, but increased the high-light-intensity failure. Emulsion (C) containing Ir also improved low illuminance failure, but lowered the appropriate exposure sensitivity. Further, when the number of carbon atoms in the substituents X and Y was 5 or more, the improvement in low illuminance failure was extremely reduced.

Example 2 A twinned thick plate emulsion (similar to emulsion (Δ)) with a legal content of 8 mol% (
D) was adjusted. However, no dye was added before chemical sensitization. The sensitizing dyes listed in Table 2 were added 30 minutes before coating. It was coated and developed in the same manner as in Example 1, and sensitometry was performed. The results are shown in Table-2.

As is clear from Table 2, the oxidation potential is 1-0.98 (
Only in the coated sample to which a sensitizing dye having a value more base than VV3SCE) and hydroquinone was added, the low light sensitivity increased and the gradation became hard.

Example 3 Into a container containing 25 g of potassium bromide, 6 g of potassium iodide, 9 cc of 2N potassium thiocyanate, and 24 g of gelatin in 1β of water, an aqueous solution of silver nitrate, potassium bromide, and an aqueous solution were added using the usual ammonia method. A silver iodobromide emulsion with an average grain size of 1.0 μm and a relatively amorphous thick plate having an iodine content of 4 mol % was prepared by adding by the double jet method, and using sodium thiosulfate and chloroauric acid. A photosensitive silver iodobromide emulsion (E
) was obtained.

(Double 1 thickness) Preparation of halogen silver milk Also, in a container containing 25 g of potassium bromide, 6 g of potassium iodide, 9 cc of 2N potassium thiocyanate, and 24 g of gelatin in 1 liter of water, a silver nitrate aqueous solution was prepared using the usual ammonia method. , an aqueous potassium iodobromide solution containing 3 g of potassium iodide was added by the double Geso I method to obtain an average particle size of 1.
A silver iodobromide emulsion with a relatively amorphous thick plate of 0 μm and an iodide content of 6 mol % was prepared, and chemically sensitized using sodium thiosulfate and chloroauric acid to give a pAg of 8.6 and a pH of 6 mol %.
A photosensitive silver iodobromide emulsion (F) of 6,4 was obtained.

In addition, 25 g of potassium bromide, 8 g of potassium iodide, 9 cc of 2N potassium thiocyanate and 24
A silver nitrate aqueous solution and a potassium iodobromide aqueous solution containing 4 g of potassium iodide were added using the usual ammonia method into a container containing 1.5 g of gelatin using the double jet method to form relatively amorphous particles with an average particle size of 1.0 μm. Almost thick plate-like with iodine content of 8
A mol% silver iodobromide emulsion was prepared and chemically sensitized using sodium thiosulfate and chloroauric acid to give a pAg of 8.6.
A photosensitive silver iodobromide emulsion (G) having a pH of 6.4 was obtained.

Preparation of a silver halide emulsion layer with an average aspect ratio of 6.5 In a container containing 5 g of potassium bromide and 30 g of gelatin in water II, add a 5% aqueous solution of silver nitrate and bromide while keeping the pA8 at 9.5. A mixed aqueous solution of potassium and potassium iodide is added, then 5% of the total silver nitrate is added by a single jet method, and the remaining 90% of the silver nitrate aqueous solution, potassium bromide and iodine are added while maintaining pAg at 8.1. A mixed aqueous solution of potassium chloride was added using a double jet method to obtain an average projected area diameter of 1.3 μm, standard deviation of 15%, and aspect ratio of 6.
．． A tabular silver iodobromide emulsion of No. 5 was prepared and chemically sensitized using sodium thiosulfate and chloroauric acid to give a pAg of 8.
A photosensitive silver iodobromide emulsion (H) having a pH of 6.4 and an iodide content of 4 mol % was obtained. Furthermore, the concentration of potassium iodide in the halogen mixed solution was increased to produce a photosensitive silver iodobromide emulsion (I) with an iodine content of 6 mol% and a photosensitive silver iodobromide emulsion (J) with an iodine content of 10 mol%. Obtained.

Emulsion (E) (F) (G) (H) (N (J) was spectrally sensitized by adding 250 μl 1 mol Ag of the following sensitizing dye before chemical sensitization.

Coating samples 88 to 99 were prepared in the same manner as in Example 1. Further, exposure and development were carried out in the same manner as in Example 1, and sensitometry was performed. The results are shown in Table-3.

Table-3 (C11□)zcHcHs (Cllz) z
cHcH303H 803° Oxidation potential 0.79 (VvsSCE Low light exposure (100 seconds) Change in sensitivity with and without B-1 Δγ-
r (0,5-0,1; B-1 addition)-γ(0,5-0
.
By adding -1, the increase in low-light sensitivity is small and the gradation does not become hard. However, in emulsions (F), (G), (T), and (J) having a legal content of 6 mol % or more, the low-light sensitivity greatly increased and the gradation became hard.

Example 4 The following formulation was coated on the support used in Example 1 using an emulsion coating process.

1st layer (bottom layer) Gelatin 0.6g/n (3, 6■
/d Polypotassium p-vinylbenzenesulfonate second layer gelatin 9■/d 1, 0g/m C1゜175■/m CH2C) 12sO3K CH2CH25O, 26■/POCII□CII□SO,K Cl1□CH2SO3 16■ /rrl HCj! 0.11■
/d 3rd layer gelatin 0.4■/d Polypotassium-p-vinylbenzenesulfonate 5■/n (9■/bo) 4th layer (emulsion layer) Particle size was adjusted to 0.5μ, before chemical sensitization Sensitizing dye l-
An emulsion (K) having a normal content of 6 mol % was prepared in the same manner as emulsion (F) except that 300 μl of 1 mol Ag of Emulsion No. 10 was added.

Coated silver amount 1.36g/% Gelatin amount 2.0g/m4-hydroxy-6-
Methyl 1.3.3a, 7-chitrazaindene 30 /, (CIBH
3SO(CH2CH20)2511 7
mg/rtrPolypotassium-p-vinylbenzenesulfonate 50■/dBis-(vinylsulfonylacetamido)ethane 57TNl/m5th layer (
Emulsion layer) The grain size was adjusted to 0.8 μ, and the sensitizing dye I-1 was adjusted to 280 μm.
(2) An emulsion (L) having a legal content of 8 mol % was used, which was prepared in the same manner as emulsion [A] except that the amount was increased to 1 mol Ag.

Coated silver amount 2.5g/m Gelatin amount 3.6g/rri4-hydroxy-
6-Methyl 1,3.3a, 7-chitrazaindene 21■/rrlC+
eHisO(CH2CH20) zsll
121W/ rrrCH: 1CH2C (CI120H
)3 190 ay/d Polybotacium p-vinylbenzene sulfone-1.44/d 6th layer Emulsion [A] was used in place of emulsion (L), and the coating was applied in the same manner as in the 5th layer.

7th layer (surface protective layer) Gelatin 0.8g/rrr13Akebono/d Polymethyl methacrylate fine particles (average particle size 3μ) 0.13■/rd Polypotassium p-vinylhenzenesulfonate 6■/M42■/d C+slh+C00C+6H+: +50■/MC,F17SO,-111-CH2COOKCI II
.

1, 8■/n (Table 4 (continued) S is the sensitivity at 10-2 seconds exposure of sample level 100
It was set to 0.

γ is r ((Fog+0.5) −(Fog+0.1)
).

For A-1 and B-1, a 20% methanol solution containing 0.2% asconbic acid was used.

As is clear from Table 4, compounds A and B of the present invention have the effect of increasing low-light sensitivity even when added to any of the constituent layers of the light-sensitive material.

The types, added layers, and amounts of compounds A and B of the present invention are shown in Table-
4. For dura mater, coated samples were heated at 25°C and 65% RH for 7 days.
After storing it for 3 days, immerse it in distilled water at 25℃ for 3 minutes.
This was done by adding vinylsulfonylacetamido)ethane.

C+:+II. 7CONIICIl□CI□-N-CI
After application of ICOO6H3 50.7%, sensitometry was carried out in the same manner as in the example.

However, development was performed as follows.

Developer: FP-50011 (manufactured by Fuji Photo Film ■) Development time: 55 seconds Development temperature: 30°C Developer solution: SPD (manufactured by Fuji Photo Film ■) Fixer
Super Fuji Fix DP (manufactured by Fuji Photo Film ■) The results are shown in Table 4.

Patent applicant Fuji Photo Film Co., Ltd. case display name of invention person who makes corrections Relationship with the incident Procedural amendment 1986 Special Application No. 262 Co., Ltd. Silver halide photographic material

Claims (1)

[Scope of Claims] A photographic material having a silver halide emulsion layer spectrally sensitized with at least one spectral sensitizing dye on a support, wherein the average iodine content of the silver halide is 6 mol%. The oxidation potential of the spectral sensitizing dye is +0.98 (V_
V_SCE) or a value less base than that, and the emulsion layer or other hydrophilic colloid layer contains the following general formula [A
A silver halide photographic material containing at least one compound selected from the compounds represented by ] and [B]. General formula (A) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ (B
)▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, X and Y are -H, -OH, -Cl, and -OM, respectively]
(M is an alkali metal ion) amino group, carboxyl group, sulfone group, sulfonamino group, sulfonated carbonyl group, carboxyamino group, alkyl group, carboxyalkyl group, sulfonated alkyl group, hydroxyalkyl group, alkyl ether group, or Represents an alkylthioether group (with 4 or less carbon atoms). X and Y may be the same or different. ]