JPH04172337A - Silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To obtain silver halide photosensitive material of high sensitivity and low photographic forgging and photo chemical sensitization in particular by providing at least one specific silver halide agent layer on a supporting body. CONSTITUTION:Selenium sensitization is applied in an arbitrary process in manufacturing emulsion, and at least one layer of silver halide agent layer containing silver halide particles including silver iodide of 5% or more on the surface of silver halide particles is provided on a supporting body. It is preferable to be deoxidized and sensitized while particles are growing. Selenium is sensitized by stirring emulsion for a specified time with unstable type selenium compound and/or not unstable selenium compound added at a high temperature. By this constitution, a high sensitive silver halide photosensitive material of low photographic fogging can be obtained through a stable manufacture.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a silver halide photographic light-sensitive material, and more specifically, the present invention relates to a silver halide photographic light-sensitive material, and more specifically, it is selenium sensitized during the manufacturing process and has a specified amount of selenium on the surface. The present invention relates to a silver halide photographic light-sensitive material containing photosensitive silver halide grains containing silver iodide, having high sensitivity and little fog, and particularly high sensitivity in the color sensitization region.

(Prior Art) The basic properties required of a silver halide emulsion for photographing are high sensitivity, low fog, and fine grain.

In order to increase the sensitivity of an emulsion, (1) increase the number of photons absorbed by a single grain; (2) increase the efficiency with which photoelectrons generated by light absorption are converted into silver clusters (latent images); and (3) it is necessary to increase the development activity in order to effectively utilize the formed latent image. Increasing the size of particles increases the number of photons absorbed by one particle, but reduces image quality. Increasing the development activity is also an effective means for increasing the sensitivity, but in the case of parallel development such as color development, graininess generally deteriorates. In order to increase sensitivity without causing deterioration of graininess, it is most preferable to increase the efficiency of converting photoelectrons into latent images, that is, to increase quantum sensitivity. In order to increase quantum sensitivity, it is necessary to eliminate inefficient processes such as recombination and latent image dispersion as much as possible. It is known that reduction sensitization, which creates small silver nuclei with no development activity inside or on the surface of silver halide, is effective in preventing recombination.

One way to increase quantum sensitivity is to efficiently perform chemical sensitization. A common method is to increase the sensitivity by sulfur sensitization, gold sensitization, or a combination thereof. Another exacerbation method is selenium sensitization.

As described in U.S. Pat. It also had drawbacks such as poor storage stability. Afterwards, attempts were made to improve the results as disclosed in Japanese Patent Application Laid-open Nos. 58-180536, 60-151637, and U.S. Patent No. 4,565,778, but no sufficient improvement effect was obtained. It has not yet been developed into a viable sensitization method.

(Problems to be Solved by the Invention) With conventional selenium sensitization techniques, it is difficult to prepare high-speed emulsions with low fog, and it is also difficult to stably prepare high-speed emulsions. Therefore, an object of the present invention is to overcome the problems of selenium sensitization technology in order to meet the recent strong demand for high sensitivity and high image quality, and to produce high-sensitivity silver halide photographs with low fog that can be stably produced. Our purpose is to provide photosensitive materials.

(Means for Solving the Problem) The above object has been achieved by the silver halide photographic material according to the present invention described below.

1) A silver halide emulsion layer containing silver halide grains that has been selenium-sensitized in any step of emulsion production and contains 5 mol % or more of silver iodide on the surface of the silver halide grains. A silver halide photographic material having at least one layer of on a support.

2) The silver halide photographic material as described in 1) above, which is reduction sensitized during grain growth.

3) The above 2) is reduction-sensitized in the presence of at least one compound represented by formula [11, [■], or (III).
The silver halide photographic material described above.

(1) R-3OzS-M (II) R-3O□S-R' [m] RS O2S L m S S O2
In the formula R'', R, R', and R'' may be the same or different and represent an aliphatic group, an aromatic group, or a heterocyclic group, and M represents a cation. L represents a divalent linking group, and m is O or 1.

The compound of general formula (1) to I[) may be a polymer containing a divalent group derived from the structure shown by [1] to III) as a repeating unit. When possible, R, R', R'', and L may be bonded to each other to form a ring.4) Sensitized in the presence of a selenium sensitizer represented by the general formula [IV]. The photographic material as described in 1), 2) or 3) above.

General formula [IV] p In the formula, Rz, R3, and R are an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group,
Aryl group, heterocyclic group, acyl group, carboxy group, alkoxycarbonyl group, aryloxycarbonyl group,
Represents a carbamoyl group or a sulfamoyl group.

However, tetramethylselenourea is excluded.

5) The silver halide photographic material as described in 4) above, wherein the general formula (IVI) is represented by the following general formula [V].

General formula (V) e II R4R in the formula Rs, R&, R? , and E is an alkyl group,
Represents a cycloalkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, heterocyclic group, acyl group, carboxy group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, and sulfamoyl group.

However, E is a group having a Hammett's substituent constant σp value of -0, 1 or more.

6) The photographic material as described in 1), 2) or 3) above, which is sensitized in the presence of a selenium sensitizer represented by general formula (Vl).

General formula [VI) e II R9RIO where R3, R4, R,. , R11 is a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a heterocyclic group, an acyl group,
Represents a carboxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, and a sulfamoyl group. However, at least one set of R1 and R9, R9 and R10, R1° and Ro, and RII and Rs shall be bonded to each other to form a ring.

The present invention will be explained in detail below.

Selenium sensitization is carried out by adding unstable selenium compounds and/or non-labile selenium compounds to high temperature, preferably 4
This is done by stirring the emulsion at 0°C or higher for a certain period of time. Selenium sensitization using an unstable selenium sensitizer described in Japanese Patent Publication No. 44-15748 is preferably used. Specific unstable selenium sensitizers include aliphatic isoselenocyanates such as allyl isoselenocyanate, selenoureas, selenoketones, selenoamides, selenocarboxylic acids and esters, and selenophosphates. Preferred unstable selenium compounds are shown below.

1. Colloidal metallic selenium ■, organic selenium compounds (selenium atoms are double bonded to carbon atoms of organic compounds through covalent bonds) a. Isoselenocyanates For example, aliphatic inselenocyanates such as allyl isoselenocyanate b Selenoureas (including enol type), such as selenourea, and methyl, ethyl, propyl, isopropyl,
Butyl, hexyl, octyl, dioctyl, tetramethyl, N-(β-carboxyethyl) -N', N'-
Aliphatic selenoureas having aliphatic groups such as dimethyl, N, N-dimethyl, diethyl, dimethyl; aromatic selenoureas having one or more aromatic groups such as phenyl, tolyl; heterocycles such as pyridyl, hendithiazolyl, etc. Heterocyclic selenourea with formula group.

C Selenoketones, e.g., selenoacetone, selenoacetopheno, ＼, selenoketone bonded to an alkyl group or /C═Se, selenohensiphenone, d Selenoamides, e.g. selenoamide e Selenocarboxylic acids and esters, e.g. 2- Selenopropionic acid, 3-selenobutyric acid, methyl 3-selenobutyrate ■, others a Selenides such as diethyl selenide, diethyl selenide, triphenylphosphine selenide b Selenophosphates such as tri-p-)lylseleno Phosphate, tri-n-butylselenophosphate Particularly preferred selenium sensitizers are described below.

General formula [IV] e In the formula, R3, Rz, Rx, and R4 are an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a heterocyclic group, an acyl group, a carboxy group, an alkoxycarbonyl group , represents an aryloxycarbonyl group, a carbamoyl group, or a sulfamoyl group.

(However, excluding tetramethylselenourea) General formula [
VI) e Rq L.

In the formula, RIl, , R7, Ro. , R1 is a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a heterocyclic group, an acyl group, a carboxy group, a formyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, Represents a sulfamoyl group. (However, RIl, R9, R3
and R1°, R1G and Ro, and at least one of R11 and R8
The sets are assumed to be combined with each other to form a ring. ) Next, general formula [IV] will be explained in detail.

In the formula, R,, R2, R3, R, are substituted or unsubstituted alkyl groups (e.g. methyl, ethyl, n-propyl, t
-butyl, isopropyl, n-octyl), substituted or unsubstituted cycloalkyl groups (e.g. cyclopentyl,
cyclohexyl, 2-methylcyclohexyl), substituted or unsubstituted alkenyl groups (e.g. allyl, 2-butenyl, 3-pentenyl), substituted or unsubstituted alkynyl groups (e.g. propargyl, 3-pentynyl), substituted or unsubstituted alkenyl groups (e.g. propargyl, 3-pentynyl) aralkyl groups (e.g. benzyl, phenethyl), substituted or unsubstituted aryl groups (e.g. phenyl, naphthyl, 4-methylphenyl), substituted or unsubstituted heterocyclic groups (e.g. pyridyl, thienyl, furyl, imidazolyl, piperidyl, morpholyl) ), substituted or unsubstituted acyl groups (e.g. acetyl, benzoyl, formyl, pivaloyl), carboxy groups, substituted or unsubstituted alkoxycarbonyl groups (e.g. methoxycarbonyl, ethoxycarbonyl), substituted or unsubstituted aryloxycarbonyl groups ( (e.g. phenoxycarbonyl), substituted or unsubstituted carbamoyl groups (e.g. carbamoyl, dimethylcarbamoyl, propylcarbamoyl), substituted or unsubstituted sulfamoyl groups (e.g. sulfamoyl, N-methylsulfamoyl)
represents.

Here, examples of substituents for Rr, Rz, Rs, and Ra include the following. These groups may be further substituted.

That is, alkyl groups (e.g. methyl, ethyl, t-butyl), cycloalkyl groups (e.g. cyclopentyl, cyclohexyl), alkenyl groups (e.g. haaryl, 3-pentenyl), alkynyl groups (e.g. propargyl, 3-pentynyl), aralkyl groups (e.g. (e.g. benzyl, phenethyl), aryl groups (e.g. phenyl, naphthyl), heterocyclic groups (e.g. pyridyl, thienyl, furyl, imidazolyl, piperidyl, morpholyl, benztriazolyl, benzoxacylyl, thiazolyl, tetrazolyl, tetraazaindenyl, indolyl), acyl groups (e.g. acetyl, benzoyl, formyl, pivaloyl), carboxy groups, alkoxycarbonyl groups (e.g. methoxycarbonyl, ethoxycarbonyl), aryloxycarbonyl groups (e.g. phenoxycarbonyl), acyl groups (e.g. acetoxy, benzoyloxy) , amino group (
For example, unsubstituted amino, dimethylamino, ethylamino)
, ammonio groups (e.g. trimethylammonio), acylamino groups (e.g. acetylamino, benzoylamino), carbamoyl groups (e.g. carbamoyl, dimethylcarbamoyl, propylcarbamoyl), sulfonylamino groups (e.g. benzenesulfonamide), sulfamoyl groups (e.g. sulfamoyl, N-methylsulfamoyl), alkoxy groups (e.g. methoxy, ethoxy, isopropoxy), aryloxy groups (e.g. phenoxy)
, alkylthio groups (e.g. methylthio, ethylthio),
Arylthio groups (e.g. phenylthio), sulfonyl groups (e.g. mesyl, benzenesulfonyl), sulfinyl groups (e.g. tLt, methylsulfinyl, ethylsulfinyl), sulfo groups, sulfino groups, hydroxy groups, halogen groups (e.g. fluoro, chloro) , bromo), cyano group, nitro group, ureido group (e.g. ureido, N'
-methylureido), phosphono group, and mercapto group.

Among the compounds represented by the general formula [IV], the following general formula [V] is preferred.

General formula Cv ] e Ra Rt In the formula, Rs , Rh , Rt , and E are alkyl groups,
Represents a cycloalkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, heterocyclic group, acyl group, carboxy group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, and sulfamoyl group.

(However, E is a group having a Hammett's substituent constant σρ value of −0.1 or more.) Next, general formula [V] will be explained in detail.

In the formula, R3, R4, R, - are R1 in the general formula [IV],
It has the same meaning as Rz, R2, R-.

E is Hammett's substituent constant, σp value (Journal
of Medicinal Chemistry” (Journal
of Medicinal Chemistry) Vol. 16, p. 304, (1973), Vol. 20, 30
4, (1977). ) is -0,1
Substituted or unsubstituted alkyl group having the above value (e.g. chloromethyl, trifluoromethyl, acetonyl)
, substituted or unsubstituted cycloalkyl groups (e.g. cyclopentyl), substituted or unsubstituted alkenyl groups (e.g. 1-chloro-3-butenyl, 1-chloro-4-octenyl), substituted or unsubstituted alkynyl groups (e.g. 1 -chloro-3-butynyl, 1-chloro-4-octenyl), substituted or unsubstituted aralkyl groups (e.g. benzyl), substituted or unsubstituted aryl! (e.g. phenyl, pentafluorophenyl), substituted or unsubstituted heterocyclic groups (e.g. 4-pyridyl, 2-benzoxasilyl, l-ethyl-2-benzimidazolyl), substituted or unsubstituted acyl groups (e.g. acetyl , formyl, benzoyl group, pivaloyl), carboxy group, substituted or unsubstituted alkoxycarbonyl group (e.g. methoxycarbonyl, ethoxycarbonyl), substituted or unsubstituted aryloxycarbonyl group (e.g. phenoxycarbonyl), substituted or unsubstituted carbamoyl Group (
(e.g., carbamoyl, dimethylcarbamoyl, propylcarbamoyl), substituted or unsubstituted sulfamoyl groups (e.g., sulfamoyl, methylsulfamoyl)
represents.

Here, the substituents for R3, R4, R, and E have the same meanings as the substituents for R, R2, R, and R4 in General II [IV).

In general formula (V), preferably L< is R3, R4, R.

is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group,
Represents a substituted or unsubstituted acyl group. E is a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted acyl group, a substituted or unsubstituted carbamoyl group, a substituted alkyl group, and a substituted or unsubstituted acyl group having a Hammett substituent constant σpffi of 0.3 or more. Aryl groups are preferred.

More preferably, R+, Rz, and Ri represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted acyl group. E is more preferably an acyl group having a Hammett's substituent constant σρ value of 0.5 or more.

Next, general formula [VI] will be explained in detail.

In the formula, R3, R4, R,. , R11 is a hydrogen atom, a substituted or unsubstituted alkyl group (e.g. methyl, ethyl, n
-propyl, t-butyl, isopropyl, n-octyl), substituted or unsubstituted cycloalkyl groups (e.g. cyclopentyl, cyclohexyl, 2-methylcyclohexyl), substituted or unsubstituted alkenyl groups (e.g. allyl, 2-butenyl, 3 -pentenyl), substituted or unsubstituted alkynyl groups (e.g. propargyl, 3-pentynyl), substituted or unsubstituted aralkyl groups (e.g. benzyl, phenethyl), substituted or unsubstituted aryl groups (e.g. phenyl, naphthyl, 4-methyl phenyl), substituted or unsubstituted heterocyclic groups (e.g. pyridyl, thienyl, furyl, imidazolyl, piperidyl, morpholyl), substituted or unsubstituted acyl groups (e.g. acetyl, benzoyl, formyl, pivaloyl), carboxy groups, substituted or Unsubstituted alkoxycarbonyl group (
For example, methoxycarbonyl, ethoxycarbonyl), substituted or unsubstituted aryloxycarbonyl groups (e.g.
i represents a substituted or unsubstituted carbamoyl group (eg, carbamoyl, dimethylcarbamoyl, propylcarbamoyl), or a substituted or unsubstituted sulfamoyl group (eg, sulfamoyl, methylsulfamoyl).

At this time, the group that is combined to form a ring may include a substituted or unsubstituted alkylene group (ether group, thioether group, substituted or unsubstituted amino group, etc.). For example, methylene, ethylene, propylene, butylene,
Hexylene, 1-methylethylene, CHzCHtOC
HzCHz-1-CHzCHJHCfhCHz-1),
A substituted or unsubstituted aralkylene group (e.g. benzylidene), a substituted or unsubstituted arylene group (e.g. phenylene, naphthylene), a substituted or unsubstituted heterocyclic chain, or a linking group combining these (for example, here Rs
, R-, R1°, and Rl 1 include those described for R3, Rz, R2, and R4 in the general formula [■]. .

In general formula (■), more preferably, the ring formed by R8 and R9, R1 and R1°, R3° and R11, R11 and R3 is a 5- or 6-membered ring, and Rs, Rs, R10, R
11 is a hydrogen atom, a substituted or unsubstituted alkyl group,
It is a substituted or unsubstituted acyl group.

Specific examples of selenium sensitizers that can be used in the present invention are shown in Table A below, but the present invention is not limited thereto.

The compounds represented by the general formulas [■] and [V] can be synthesized according to already known methods. That is, 5
aul Patai (ed.), [The chemistry of organic selenium and tellurium combined J]
nic selenium and tellur
iuai co+mounds) Volume 2, pages 255~
It can be synthesized by the method described on page 258 (19B7).

Next, the methods for synthesizing the compounds of general formulas [IV] and [V] will be explained by giving typical synthetic examples.

Synthesis Example 1 Synthesis of Compound IV-1 1-(1) Synthesis of N-acetyl-N,N',N'-)limethylthiourea A solution of 740 g of N,N,N'-1-limethylthiourea in toluene 400+1 Add 37 g of acetic anhydride, and
0.5all of concentrated sulfuric acid was added while stirring. 8 of the reaction solution
Warmed to 0°C, stirred for 6 hours, cooled to room temperature, and stirred for 4 hours.
00sj! Salt was added to the extracted aqueous layer to obtain a saturated saline solution. Thereafter, extraction was performed with acetonitrile, and the acetonitrile layer was dried over magnesium sulfate and concentrated to obtain the desired product.

Yield 42g Oil 1-(2) Synthesis of N-acetyl-N,N',N',S-tetramethylthiouronium iodide N-acetyl-N,N',N' obtained in 1-(1) −
42 g of trimethylthiourea was dissolved in 90 g of iodomethane and stirred at room temperature for 8 hours. Filter the formed crystals,
The desired product was obtained by washing with chloroform.

Yield: 23 g 1-(3) Synthesis of Compound IV-1 Under a nitrogen atmosphere, 2.0 g of selenium was added to 150 μl of dry ethanol, and after cooling to 0°C, 1.0 g of sodium borohydride was added with stirring. .

Gas started to form immediately and subsided after a few minutes.

Stir for a few more minutes at room temperature to remove the pale red NaH5e.
A solution was obtained. Next, add N-acetyl-N to this solution.

Add 50all of an ethanol solution of 4.0g of N',N',S-tetramethylthiouronium iodide,
It was left at room temperature for 20 hours. After adding glacial acetic acid to make the mixture slightly acidic, it was concentrated to 70-2 under reduced pressure.

The concentrated solution was extracted with chloroform and water, and the chloroform layer was concentrated to dryness. The obtained crystals were recrystallized from a mixed solvent of ethyl acetate-hexane (15 all, 10 s+f, respectively) to obtain 12.3 g of the desired exemplary compound (1).

The nuclear magnetic resonance spectrum, mass spectrum, and elemental analysis of the target product were consistent with expectations.

Yield 80% Melting point 87-88°C Synthesis Example 2 Synthesis of Compound V-29 2-(1) Synthesis of N,N'-dimethylethylenethiouronium iodide Add 20g of N,N'-dimethylethylenethiourea to an acetone solution. 30 g of iodomethane was added and stirred at room temperature for 8 hours. The generated crystals were collected by filtration and washed with acetone to obtain the desired product.

Yield: 32 g 2-(2) Synthesis of Compound V-29 From 4.0 g of N,N'-dimethylethylenethiouronium iodide obtained in 2-(1), the desired exemplary compound was prepared in the same manner as in Synthesis Example 1. 2.0g of v-29 was obtained. The nuclear magnetic resonance spectrum, mass spectrum, and elemental analysis of the target product were consistent with expectations.

Yield 76% Melting point 144-145°C Other exemplified compounds can also be synthesized in the same manner as these synthesis examples.

Until now, no specific example has been reported in which the compounds of general formulas [IV] and (V) are used as selenium sensitizers. Therefore, it was extremely difficult to predict the exacerbation effects, capri, and other photographic effects caused by these compounds, but by using the compounds of the present invention, remarkable effects could be obtained.

The amount of selenium sensitizer used in the present invention varies depending on the selenium compound used, silver halide grains, chemical ripening conditions, etc., but is generally 10 -
About 10-4 mol, preferably about 10-' to 10-5 mol is used.

The conditions for chemical sensitization in the present invention are not particularly limited, but the pHg is 6 to 11, preferably 7 to 10,
More preferably, it is 7 to 9.5, and the temperature is 40 to 9.5.
95°C, preferably 50 to 85°C.

In the present invention, it is preferable to use a noble metal sensitizing side such as tellurium, gold, platinum, palladium, and iridium in combination.

In particular, it is preferable to use a gold sensitizer in combination, and specific examples thereof include chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, gold selenide, etc. About 7 to 10 −2 moles can be used.

In the present invention, it is also preferable to use sulfur sensitization in combination. Specifically, thiosulfates (e.g. hypo),
Known unstable sulfur compounds such as thioureas (e.g. diphenylthiourea, triethylthiourea, allylthiourea) and rhodanines can be mentioned, and it is possible to use about 10-' to 10-2 mol per mol of silver halide. can.

Further, in the present invention, it is preferable to carry out selenium sensitization in the presence of a silver halide solvent.

Specifically, thiocyanates (e.g., potassium thiocyanate), thioether compounds (e.g., U.S. Pat.
No. 021215, No. 3271157, Special Publication No. 1986-3
No. 0571, the compounds described in JP-A-60-136736, especially 3,6-cythia-1.8-octanediol)
, tetrasubstituted thiourea compounds (e.g., Japanese Patent Publication No. 59-118
No. 92, compounds described in U.S. Pat. No. 4,221,863,
In particular, tetramethylthiourea), and furthermore,
Thione compound described in No. 1341, Japanese Patent Publication No. 63-297
Mercapto compound described in No. 27, JP-A-60-163
Mesoionic compounds described in US Pat. No. 042, US Pat. No. 478
Selenoether compound described in No. 2013, JP-A-2-
Examples include telluroether compounds and sulfites described in No. 118566. Among these, thiocyanates, thioether compounds, tetrasubstituted thiourea compounds and thione compounds are particularly preferably used. The amount used can be about 10-5 to 5×10-'' moles per mole of silver halide.

It was completely unexpected that the surface of the silver halide grains of the present invention contained 5 mol % or more of silver iodide, thereby making the above-mentioned selenium sensitization effect more pronounced. Various conventionally known methods can be employed to control the silver iodide content near the surface of the grains. A method in which an aqueous solution of a water-soluble silver salt and an aqueous solution of a halide containing a water-soluble iodide are further added to silver halide grains grown in the presence of a protective colloid; Addition method: A method can be selected from among the methods of adding and ripening a sparingly soluble iodide such as silver iodide or silver iodobromide. Alternatively, a method may be used in which iodide is distributed near the surface by physically ripening silver halide grains containing iodide.

It is preferable that 5 to 30 mol % of silver iodide contained on the surface of the silver halide grains of the present invention be as uniform as possible on the surface in the case of cubic or octahedral crystals. It is preferable that the grain has a layered structure in which the entire surface is covered with a layer containing silver iodide. However, in grains such as tetradecahedrons in which 111) and (100) planes coexist, or in grains such as tabular grains in which main planes and side surfaces coexist, only specific planes are mainly covered with a layer containing silver iodide. It is also a preferred form of the present invention. In other words, the present invention also includes cases where not all but part of the surface of the grain is covered with a layer containing silver iodide.

In the present invention, when forming a layer whose surface contains 5 mol% or more of silver iodide, spectral sensitizing dyes such as cyanine and merocyanine, or anti-fog agents and stabilizers such as mercapto compounds, azole compounds, and azaindene compounds are used. It is a preferred method to have it present. Similarly, thiocyanic acid,
The presence of silver halide solvents such as thioethers, ammonia, etc. may also be preferred.

The silver iodide content on the surface of silver halide grains in the present invention can be detected by various surface elemental analysis means. XPS
It is useful to use methods such as , Auger electron spectroscopy, ISS, etc. XP is the simplest and most accurate method.
S (X-ray Photoel-ectron
5 pectroscopy), and the surface silver iodide content in the present invention is defined by the value measured by this method.

X P S (X-ray Photoelectr
The depth that can be analyzed using the surface analysis method (on 5 pectroscopy) is said to be about 10 people.

Regarding the principle of the XPS method used to analyze the iodine content near the surface of silver halide grains, please refer to "Electron Spectroscopy" by Atsushi Aihara et al. (Kyoritsu Library 16, published by Kyoritsu Shuppan, 1978). can do.

The standard measurement method for XPS is
This is a method of observing the intensity of photoelectrons (usually I 3ds/z, Ag 3dszz) of iodine (1) and silver (Ag) emitted from silver chloride grains in an appropriate sample format. .

To determine the iodine content, a calibration curve of the photoelectron intensity ratio of iodine (I) and silver (Ag) (Intensity (■) 7 Intensity (Ag)) is calculated using several types of standard samples with known iodine contents. can be calculated from this calibration curve. In silver halide emulsions, gelatin adsorbed on the surface of silver halide grains is decomposed and removed using proteolytic enzymes, etc., and then
A measurement of S must be made.

In the present invention, silver halide whose grain surface contains 5 mol% or more of silver iodide refers to emulsion grains contained in one emulsion,
Refers to a material whose surface has a silver iodide content of 5 mol% or more when analyzed by elemental analysis.

In this case, if two or more types of emulsions are clearly mixed, it is necessary to perform an appropriate pretreatment such as centrifugation or furnace separation before analyzing the same type of emulsion. More preferably, it refers to an emulsion having a silver iodide content of 5 to 30 mol% when measured by standard XPS.

The effect of the present invention is remarkable when the surface of the grain contains 5 mol% or more of silver iodide;
More preferred are grains whose surfaces contain 10 to 15 mol % of silver iodide.

The surface halogen composition other than silver iodide is preferably silver bromide, but may also contain up to 10 mol % of silver chloride.

In producing the silver halide grains of the present invention, reduction sensitization is preferably carried out during the growth of the silver halide grains. Growing means that silver halide grains are undergoing physical ripening, addition of water-soluble silver salt and water-soluble alkali halide (precipitation, P
Recipe tat 1 on) is also meant to include during the further precipitation step after reduction sensitization with these additions temporarily stopped.

Reduction sensitization in the present invention refers to a method of adding a reduction sensitizer to a silver halide emulsion, and a method of adding a reduction sensitizer to a silver halide emulsion, which is called silver ripening.
A method of growing or aging in a low pl'1g atmosphere of 7, a high pH of 8 to 11 called high pH ripening.
Either a method of growing in an H atmosphere or a method of aging can be selected. Moreover, two or more methods can also be used together.

The method of adding a reduction sensitizer is a preferred method since the level of reduction sensitization can be finely adjusted.

Known reduction sensitizers include stannous salts, amines and polyamines, hydrazine derivatives, formamidine sulfinic acid, silane compounds, borane compounds, ascorbic acid and its derivatives.

For reduction sensitization in the present invention, these known reduction sensitizers can be selected and used, or two or more types of compounds can also be used in combination. Preferred compounds as reduction sensitizers include stannous chloride, thiourea dioxide, dimethylamine borane, and ascorbic acid.

The amount of reduction sensitizer added depends on the emulsion manufacturing conditions, so it is necessary to select the amount added, but it is 10-10% per mole of silver halide.
A range of 7 to 10-3 moles is suitable.

Reduction sensitizers include water, alcohols, glycols,
Dissolved in solvents such as ketones, esters, and amides,
Added during grain growth. It may be added to the reaction vessel in advance, but it is preferable to add it at an appropriate time during particle growth. Alternatively, a reduction sensitizer may be added in advance to an aqueous solution of a water-soluble silver salt or a water-soluble alkali halide, and these aqueous solutions may be used to precipitate silver halide grains. It is also preferable to add the solution of the reduction sensitizer in several portions as the particles grow, or to add the solution continuously over a long period of time.

To explain in more detail the compounds of general formula (I), CII) and [I[I] that are coexisting in the above reduction sensitizer, R,
When R' and R2 are aliphatic groups, they are saturated or unsaturated, linear, branched or cyclic aliphatic hydrocarbon groups, preferably alkyl groups having 1 to 22 carbon atoms, or 2 carbon atoms. These are 22 alkenyl groups and alkynyl groups, which may have a substituent. Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, hexadecyl, octadecyl, cyclohexyl, isopropyl, and t-butyl.

Examples of the alkenyl group include allyl and butenyl.

Examples of the alkynyl group include propargyl and butynyl.

The aromatic groups for R, R' and R2 include monocyclic or condensed ring aromatic groups, preferably those having 6 to 20 carbon atoms, such as phenyl and naphthyl. These may be substituted.

The heterocyclic group of R, R' and R2 includes nitrogen, oxygen,
3 to 1 having at least one element selected from sulfur, selenium, and tellurium and having at least one carbon atom
A 5-membered ring, preferably a 3- to 6-membered ring, such as pyrrolidine, piperidine, pyridine, tetrahydrofuran, thiophene, oxazole, thiazole, imidazole, benzothiazole, benzoxazole, benzimidazole, selenazole, benzoselenazole, Tetrazole, triazole, benzotriazole,
Examples include tetrazole, oxadiazole, and thiadeazole rings.

Substituents for R, R1 and R2 include, for example, alkyl groups (e.g. methyl, ethyl, hexyl), alkoxy groups (e.g. methoxy, ethoxy, octyl), aryl groups (e.g. phenyl, naphthyl, tolyl), hydroxyl groups. , halogen atoms (fluorine, chlorine, bromine, iodine),
Aryloxy groups (e.g. phenoxy), alkylthio groups (e.g. methylthio, butylthio), arylthio groups (e.g. phenylthio), acyl groups (e.g. acetyl, propionyl, butyryl, valeryl), sulfonyl groups (e.g. methylsulfonyl, phenylsulfonyl) ), acylamino group (e.g. acetylamino, benzoylamino), sulfonylamino group (e.g. methanesulfonylamino, henzenesulfonylamino), acyloxy group (e.g. acetoxy, benzoxy), carboxyl group, cyano group, sulfo group, amino group, -5(hSM
group, -SO□R+ group.

The divalent linking group represented by is an atom or atomic group containing at least one selected from C, N, S and 0. Specifically, for example, alkylene group, alkenylene group, alkynylene group, arylene group, -〇-1-3
, 7NH~, -CO-1-8O□-, alone or in combination.

L is preferably a divalent aliphatic group or a divalent aromatic group. As the divalent aliphatic group of L, for example, +CHz→=
(n=1-12), CL CH=C)l
CHz-1CHZCECCHz-1 can be mentioned. Examples of the divalent aromatic group for L include phenylene and naphthylene.

These substituents may be further substituted with the substituents described above.

M is preferably a metal ion or an organic cation. Examples of metal ions include lithium ions, sodium ions, and potassium ions. Examples of organic cations include ammonium ions (eg, ammonium, tetramethylammonium, tetrabutylammonium), phosphonium ions (tetraphenylphosphonium), and guanidyl groups.

When the general formula CI) or I[[) is a polymer,
Examples of the repeating unit include the following.

+CH-CH2÷C0zCHzCHzOCHzCHzSO□SM These polymers may be homopolymers or may be copolymers with other copolymers.

Specific examples of the compounds represented by the general formula (1), (II) or (I[[) are listed in Table 8 below, but the invention is not limited thereto.

The compound of general formula CI) is disclosed in JP-A-54-1019 i British Patent No. 972+211; Journal of O
rganic Chemistry (Journal of Organic Chemistry) Volume 53, Page 396 (19
88) and Che+5ical Abstracts (
It can be easily synthesized by the method described or cited in Chemical Abstracts, Vol. 59, 9776e.

Compounds of the general formula CI), (II) or (III) contain from 10-7 to 10-' per mole of silver halide.
Preferably, it is added in moles. Further 10-' to 10-
2, especially 10-' to 10-3 moles of Ag are preferred.

In order to add the compounds represented by the general formulas [■] to (III) during the manufacturing process, methods commonly used for adding additives to photographic emulsions can be applied.

For example, for water-soluble compounds, make an aqueous solution of an appropriate concentration,
Compounds that are insoluble or sparingly soluble in water are dissolved in a suitable organic solvent that is miscible with water, such as alcohols, glycols, ketones, esters, amides, etc., and does not adversely affect photographic properties. However, it can be added as a solution.

The compound represented by compound (1), (II) or (III) may be present at any stage of reduction sensitization during grain growth. Preferably, the compound is added before or during reduction sensitization. It is particularly preferable to add it so that it coexists with the reduction sensitizer.

The most preferred general formula of the compound for the present invention is a compound represented by general formula [1].

The average silver halide composition of the entire silver halide grain in the present invention is silver iodobromide or silver iodochlorobromide containing 1 to 30 mol % of silver iodide. It preferably contains 7 to 20 mol% silver iodide and 10 mol% or less silver chloride.

The silver halide grains used in the present invention may be normal crystals that do not contain twin planes.
Examples such as those explained in I (Corona Publishing, P, 163), such as single twins containing one twin plane, parallel multiple twins containing two or more parallel twin planes, and non-parallel twins. Depending on the purpose, it can be selected and used from non-parallel multiple twin crystals containing two or more planes. In the case of normal crystals, it is a cube consisting of (100) planes, an octahedron consisting of (111) planes, and
42737 and JP-A No. 60-222842, dodecahedral particles consisting of (110) planes can be used. Furthermore, Journal of Imaging
(211) as reported in 5science Vol. 30, p. 247 (1986) is representative (hl)
A surface particle, (hhl) surface particle represented by (331), (
(hkO) plane particles represented by (210) plane, and (3
(hkl) plane particles, which are represented by 21) planes, also require some ingenuity in the preparation method, but can be selected and used depending on the purpose. (
14 where 100) plane and (111) plane coexist in one particle
Particles with two or many surfaces coexisting can also be used depending on the purpose, such as hedral particles, particles with both (100) and (110) planes, or particles with (111) and (110) planes. You can choose and use it.

The grain size of the silver halide grains in the present invention is all 0.
．． The particles may be fine particles of 1 micron or less or large particles with a projected area diameter of up to 10 microns, and may be a monodisperse emulsion with a narrow distribution or a polydisperse emulsion with a wide distribution.

A so-called monodisperse silver halide emulsion having a narrow grain size distribution in which 80% or more of all grains fall within ±30% of the average grain size in terms of grain number or weight can be used in the present invention. In addition, in order to satisfy the target gradation of a light-sensitive material, two or more types of monodisperse silver halide emulsions with different grain sizes are mixed in the same layer or in separate layers in emulsion layers having substantially the same color sensitivity. Can be applied in multiple layers. Furthermore, two or more types of polydisperse silver decagenide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion may be mixed or used in a layered manner.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Grafkide, published by Paul Montell (P.

Glafkides, Chimie et Physi
que Photography Paul Mo
Ntel, 1967), "Photographic Emulsion Chemistry" by Duffin
, Published by Focal Press (G, F, Duffin Ph
otographicEmulsion Cheo+1
try (Focal Press 1966)
, Zelikman et al., "Production and Coating of Photographic Emulsions," published by Focal Press (V.L., Zelikman et al.
, Making and Coating Photog
rapic Emulsion, Focal Pr
ess.

(1964) and others. That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the methods for reacting the soluble root salt with the soluble halogen salt include the one-sided mixing method, the simultaneous mixing method,
Any combination thereof may be used. It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method). As one type of simultaneous mixing method, a method in which the 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 having a regular crystal shape and a nearly uniform grain size can be obtained.

The silver halide emulsion consisting of the regular grains described above can be obtained by controlling pAg and pH during grain formation. For more information, please see Photographic Science and Engineering.
5icence and Engineering) Volume 6, pp. 159-165 (1962); Journal
Op Photographic Science (Journal
of Ph-otographic 5science
), vol. 12, pp. 242-251 (1964),
U.S. Patent No. 3,655,394 and British Patent No. 1,
No. 413,748.

Further, tabular grains having an aspect ratio of 3 or more can also be used in the present invention. Tabular grains are described in ``Theory and Practice of Photography'' by C1eve, Photogra-
Phy Theory and Practice (1
930) ), p. 131; Gatoff, Photographic Science and Engineering (Cut
Off, Photographic Science
and Engineering), Volume 14, 248
~257 pages (1970); U.S. Patent No. 4,434,2
No. 26, No. 4,414,310, No. 4,433,04
No. 8, No. 4,439,520 and British Patent No. 2.1
It can be easily prepared by the method described in No. 12.157. When tabular grains are used, there are advantages such as increased covering power and increased color sensitization efficiency by sensitizing dyes, and as described in the above-cited U.S. Pat. No. 4,434,22.
This is detailed in issue 6.

Tabular grains are preferred as the emulsion used in the present invention. In particular, particles with an aspect ratio of 3 to 8 account for 50% of the total projected area.
% or more of tabular grains are preferred.

The crystal structure may be --like, the inside and outside may have different halogen compositions, or it may have a layered structure. These emulsion grains are described in British Patent No. 1,027,1
No. 46, U.S. Patent No. 3,505,068, U.S. Patent No. 4,44
No. 4,877 and Japanese Unexamined Patent Publication No. 143331/1984. Furthermore, silver halides having different compositions may be bonded by epitaxial bonding, or compounds other than silver halide such as silver rhodan or lead oxide may be bonded.

The silver halide emulsion of the present invention preferably has a distribution or structure in terms of halogen composition in its grains.

Typical examples include halogen compositions in which the interior and surface layers of particles are different, as disclosed in Japanese Patent Publications No. 43-13162, No. 61-215540, No. 60-222845, No. 61-75337, etc. These are core-shell type or double-structured particles.

In such particles, the shape of the core portion and the shape of the entire body including the shell may be the same or different. Specifically, the core part has a cubic shape, and the shape of the shelled particle may be cubic or octahedral. Conversely, the core may be octahedral and the shelled particle may be cubic or octahedral.

In addition, although the core part is a clearly regular particle, the shape of the shelled particle is slightly shifted (sometimes it is irregular or irregular).
It is possible to form a triple structure as disclosed in Japanese Patent Application No. 22844 or a multilayer structure of more than that, or to apply a thin layer of silver halide having a different composition to the surface of a core-shell double structure grain.

In order to give a structure to the inside of a particle, it is possible to create a particle having not only the above-mentioned enveloping structure but also a so-called bonding structure. These examples are disclosed in Japanese Patent Application Laid-Open No. 59-13354.
0, Japanese Patent Publication No. 58-108526, EP199290A2
, Japanese Patent Publication No. 58-24772, Japanese Patent Publication No. 59-16254
etc. are disclosed. The crystal to be bonded has a composition different from that of the host crystal, and can be bonded to an edge, a corner portion, or a surface portion of the host crystal to form a property.

Such a bonded crystal can be formed even if the host crystal is uniform in terms of halogen composition or has a core-shell structure.

In the case of a bonded structure, a combination of silver halides is naturally possible, but a bonded structure can be obtained by combining a silver halide with a silver salt compound that does not have a rock salt structure, such as silver rhodan or silver carbonate. Further, non-silver salt compounds such as PbO may also be used if a bonded structure is possible.

In the case of grains such as silver iodobromide having these structures, for example, in core-shell type grains, the silver iodide content in the core portion is preferably higher than that in the shell portion. Conversely, the grains may have a low silver iodide content in the core part and a high content in the shell part. Similarly, grains having a bonded structure may be grains in which the silver iodide content of the host crystal is high (or grains in which the silver iodide content of the bonded crystal is relatively low), or vice versa.

In addition, the boundaries between particles with these structures with different halogen compositions may be clear boundaries, or may be unclear boundaries formed by forming mixed crystals due to the difference in slope, or may be actively formed. It may also be one with continuous structural changes.

The silver halide emulsion used in the present invention is EP-009672.
7Bl, EP-0064412B1, etc., or D
E-2306447C2, Time Open I! 60-22132
Surface modification as disclosed in 0.0 may also be carried out.

The silver halide emulsion used in the present invention is preferably a surface latent image type emulsion, but an internal latent image type emulsion can also be used by selecting the developer or development conditions, as disclosed in JP-A-59-133542. can. A shallow internal latent image type emulsion covered with a thin shell can also be used depending on the purpose.

Silver halide solvents are useful to accelerate ripening. For example, it is known to have an excess of halogen ions present in the reactor to promote ripening. It is therefore clear that ripening can be accelerated simply by introducing a halide salt solution into the reactor. Other ripening agents can be used, and these ripening agents can be incorporated in their entirety into the dispersion medium in the reactor before the silver and halide salts are added, and one or more ripening agents can be used. can also be introduced into the reactor along with the addition of halide salts, silver salts or peptizers. As a further variant, the ripening agent can also be introduced independently at the halide salt and silver salt addition stages.

As ripening agents other than halogen ions, ammonia or amine compounds, thiocyanate salts such as alkali metal thiocyanate salts, especially sodium and potassium thiocyanate salts, and ammonium thiocyanate salts can be used.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing capri during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. Namely, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptohenzothiazoles, mercaptohenzimidazoles, mercaptothiadiazoles. mercaptotetrazoles (especially l-phenyl-5-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinthione; azaindenes, There are many compounds known as antifoggants or stabilizers, such as triazaindenes, tetraazaindenes (particularly 4-hydroxy-substituted (1,3,3a,7)tetraazaindenes), pentaazaindenes. compounds can be added. U.S. Patent No. 3,954,474
No. 3.982.947, Special Publication No. 52-28, 66
Those described in No. 0 can be used.

The photographic emulsion used in the present invention is preferably spectral enhanced by methine dyes or the like in order to achieve the effects of the present invention. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.

Particularly useful dyes include cyanine dyes, 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. Namely, pyrroline, oxazoline, thiozoline, pyrrole, oxazole, thiazole, selenazole, imidazole, tetrazole, pyridine, etc.; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and an aromatic hydrocarbon ring fused to these nuclei For example, indolenine, benzindolenine, indole, benzoxadole, naphthoxazole, benzothiazole, naphthothiazole, benzoselenazole, benzimidazole, and quinoline are applicable. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes contain, for example, pyrazoline-
5- to 6-membered heterocyclic nuclei of 5-one, thiohydantoin, 2-thioxapridine-2,4-dione, thiazolidine-2,4-dione, rhodanine, and thiobarbic acid can be used.

These sensitizing dyes may be used alone or in combination, and combinations of enhancing dyes are often used particularly for the purpose of supersensitization. A typical example is US Patent 2
, No. 688,545, No. 2,977.229, No. 3,
No. 397,060, No. 3.522.052, No. 3.5
No. 27,641, No. 3,617,293, No. 3,62
No. 8,964, No. 3,666.480, No. 3.672
．． No. 898, No. 3,679,428, No. 3,703,
No. 377, No. 3,769,301, No. 3,814,6
No. 09, No. 3,837,862, No. 4.026.70
No. 7, British Patent No. 1,344,281, No. 1.5 (17
, 8 (No. 13, Special Publication No. 43-4936, No. 53-12)
．． No. 375, JP-A-52-110,618, JP-A-52-110, No. 52-
No. 109.925.

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.

The sensitizing dye may be added to the emulsion at any stage of emulsion preparation known to be useful. Most commonly, it is carried out after the completion of chemical sensitization and before coating, but US Patent No. 3,628,969
It is also described in JP-A-58-113.928 that spectral sensitization can be carried out at the same time as chemical sensitization by adding a chemical sensitizer at the same time as described in JP-A-58-113.928. It can be carried out prior to chemical sensitization as described above, or it can be added before the completion of silver halide grain precipitation to start spectral sensitization. Furthermore, US patent tube 4
．． 225,666 by adding these said compounds separately, i.e., some of these compounds are added prior to chemical sensitization and the rest are added after chemical sensitization. Also possible, U.S. Patent No. 4, 183.
No. 756, or at any time during silver halide grain formation.

The amount added is 4X10-' to 8 per mole of silver halide.
X10-3 moles can be used, but for a more preferred silver halide grain size of 0.2 to 1.2 .mu.m, about 5X1O-5 to 2X10" moles are more effective.

In addition to the various additives described above, various additives may be used in the light-sensitive material of the present invention depending on the purpose.

These additives are described in more detail in Research Disclosure+-Item 17643 (December 1978) and Item 18716 (November 1979).
The relevant sections are summarized in the table below.

2 Sensitivity increasing agent Same as above 4 Brightening agent Page 24 Filter dye 25-26R 7 Stain inhibitor Page 25 Right column 650 Page Left to right column 8
Dye image stabilizer Page 25 9 Hardener Page 26 Page 651 Left column 10 Binder Page 26 Same as above 11 Plasticizer, lubricant Page 27 Page 650 Right column Various color couplers can be used in the present invention, and their specific details are An example is the aforementioned research disc o −';
(RD) N1117643, 2-c-c.

As a yellow coupler, for example, U.S. Patent Tube 3.93
3.501, 4.022.620, 4.3
No. 26.024, No. 4.4OL752, Special Publication No. 1983
Preferred are those described in British Patent No. 10739, British Patent No. 1.425.020, and British Patent No. 1.476.760.

As the magenta coupler, 5-pyrazolone and pyrazoloazole compounds are preferred, such as U.S. Pat.
, 310.619, 4,351,897, European Patent No. 73,636, U.S. Patent No. 3,061,432
No. 3,725. ．． No. 067, Research Disclosure NLIL 24220 (June 1984), JP 60-33552, Research Disclosure NLIL 24230 (June 1984), JP 60-4
3659, U.S. Patent No. 4,500,630, U.S. Patent No. 4
, 540, 654 are particularly preferred.

Cyan couplers include phenolic and naphthol couplers, such as those described in U.S. Patent No. 4.052.
No. 212, No. 4.146,396, No. 4,228
, No. 233, No. 4, No. 296, No. 200, No. 2.
No. 369,929, No. 2.801.171, No. 2
．． 772.162, 2,895,826, 3,772.002, 3,758,308, 4.334,011, 4.327.173,
West German Patent Publication No. 3.329.729, European Patent No. 12
1.635A, U.S. Patent No. 3.446.622, U.S. Patent No. 4.333,999, U.S. Patent No. 4.451,559,
4.427.767, European Patent No. 161.626
Those described in item A are preferred.

Colored couplers for correcting unnecessary absorption of coloring dyes are available, for example, in Research Disclosure No. 17.
Section 643 ■-G, U.S. Patent Box 4,163,670,
Special Publication No. 57-39413, U.S. Patent Box 4,004,9
No. 29, No. 4.138.258, British patent cylinder 1,1
46,368 is preferred.

Couplers whose coloring dyes have appropriate diffusivity include, for example, U.S. Patent No. 4,366.237, British Patent No. 2,
125,570, European Patent No. 96,570 and West German Patent Publication No. 3,234,533 are preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat. No. 3,451,820, U.S. Pat.
It is described in No. 173, etc.

Couplers that release photographically useful residues upon camping can also be preferably used in the present invention. DIR couplers that release development inhibitors include, for example, the above-mentioned RD17.
643, patents described in sections ■ to F, JP-A-57-1
No. 51944, No. 57-154234, No. 60-18
No. 4,248, US Pat. No. 4,248,962 are preferred.

As a coupler that releases a nucleating agent or a development accelerator imagewise during development, for example, British Patent No. 2.097.14
No. 0, No. 2.13L No. 188, JP-A-59-157
Those described in No. 638 and No. 59-170840 are preferred.

Other couplers that can be used in the photosensitive material of the present invention include, for example, the competitive couplers described in U.S. Patent No. 4,130,427, and U.S. Pat.
No. 4, 338, 393, No. 4,310,
Polygonal coupler described in No. 618 etc., JP-A-60-18
5950, JP-A No. 62-24252, etc. DIR Ftx compounds or DIR coupler-releasing couplers or DIR coupler-releasing couplers or redoxes, couplers that release dyes that change color after separation as described in European Patent No. 173,302A. , for example R, D, Nα1144
9, No. 24241, and bleach accelerator-releasing couplers described in JP-A-61-201247, e.g., U.S. Pat.
53,477, and the like.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027 and others.

The boiling point at normal pressure used in the oil-in-water dispersion method is 175°C.
Specific examples of the above-mentioned high-boiling organic solvents include phthalic acid esters (e.g., dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate), esters of phosphoric acid or phosphonic acid (e.g., phenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate), benzoic acid esters (e.g. 2-ethylhexyl phosphate),
Ethylhexylhenshade, dodecylbenzoate,
2-ethylhexyl-P-hydroxyhenzoate),
Amides (e.g., N,N-diethyldodecanamide,
N,N-diethyl laurylamide, N-tetradecylpyrrolidone), alcohols or phenols (e.g. isostearyl alcohol, 2,4-ditert
-amylphenol), aliphatic carboxylic acid esters (
For example, bis(2-ethylhexyl)sepacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate), aniline derivatives (for example, N,N-dibutyl-2-butoxy-5-tert-octylaniline) ), hydrocarbons (
Examples include paraffin, dodecylhensen, and diisopropylnaphthalene. In addition, as an auxiliary solvent,
boiling point of about 30°C or more, preferably about 50°C or more
Organic solvents having a temperature of 0°C or lower can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexane, 2-ethoxyethyl acetate, and dimethylformamide.

The process and effects of latex dispersion methods and specific examples of latex for impregnation are described in U.S. Pat. Are listed.

The present invention can be applied to various color photosensitive materials. Typical examples include color negative film for general use or movies, color reversal film for slides or television, color paper, color positive film, and color reversal paper.

When the present invention is used in color photographic materials, it can be applied to photosensitive materials with various configurations and photosensitive materials in which layer configurations and special color materials are combined.

A typical example is illustrated below. JP 47-49031, JP 49-3843, JP 50-21248, JP 59-38147, JP 59-60437,
JP 60-227256, JP 61-4043, JP 61-43743, JP 61-42657
This is a combination of the coupling speed and diffusivity of color couplers and the layer structure, as shown in No. Tokuko Sho 49-154
No. 95, U.S. Pat. No. 3,843,469, in which the same color-sensitive layer is divided into two or more layers, Japanese Patent Publication No. 53-3701
No. 7, Special Publication No. 53-37018, Japanese Patent Publication No. 51-490
No. 27, JP-A-52-143016, JP-A-53-9
No. 7424, JP-A-53-97831, JP-A-62-
200350 and JP-A-59-177551, which specify the arrangement of high-sensitivity layers and low-sensitivity layers and the arrangement of layers with different color sensitivities.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, page 28 of NQ17643, and Nn1871 of the same
6, from the right column on page 647 to the left column on page 648.

The color photographic material according to the present invention includes the above-mentioned RD,
No. 17643, pages 28-29, and Nα187 of the same.
16, page 651, left column to right column.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but p-phenylenediamine compounds are preferably used, representative examples of which include 3-methyl-4-amino-N, N-diethylaniline, 3- Methyl-4-amino-N-ethyl-N
-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N
-β-methoxyethylaniline and their sulfates, hydrochlorides, p-)luenesulfonates, and the like. Two or more of these compounds can be used in combination depending on the purpose.

The color developer may contain p8 buffers such as alkali metal carbonates, borates or phosphates, bromide salts, iodide salts,
Development inhibitors or antifoggants such as benzimidazoles, benzothiazoles or mercapto compounds are generally included. In addition, as necessary, various compounds such as hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenyl semicarbazides, triethanolamine, catechol sulfonic acids, and triethylenediamine (1,4-diazabicyclo(2,2,23 octyne)) may be added. Preservatives, organic solvents such as ethylene glycol, diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts,
Development accelerators such as amines, dye-forming couplers, competitive couplers, fogging agents such as sodium boron hydride, auxiliary developing agents such as l-phenyl-3-pyrazolidone, tackifiers, aminopolycarboxylic acids, aminopolymer Various calcinants such as phosphonic acid, alkylphosphonic acid, and phosphonocarboxylic acid, such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, and 1-hydroxy Ethylidene
1,1-diphosphonic acid, nitrilo-N,N,N-)rimethylenephosphonic acid, ethylenediamine-N,N,N'
, N'-tetramethylenephosphonic acid, ethylene glycol (0-hydroxyphenylacetic acid), and salts thereof.

Further, when performing reversal processing, black and white development is usually performed and then color development is performed. This black and white developer contains known black and white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol. It can be used alone or in combination.

These color developing solutions and black and white developing solutions generally have a pH of 9 to 12. The amount of replenishment of these developing solutions depends on the color photographic light-sensitive material to be processed, but it is generally less than 31 per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher,
It can also be less than f. When reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the area of contact with the air in the processing tank. Furthermore, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

The time for color development processing is usually set between 2 and 5 minutes, but the processing time can be further shortened by using high temperature, high pH, and high concentration of color developing agent.

After color development, the photographic opalescent layer is usually bleached.

The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or separately. Furthermore, in order to speed up the processing, a processing method may be used in which bleaching is followed by bleach-fixing. Furthermore, treatment in two continuous bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment can be carried out as desired depending on the purpose. Examples of bleaching agents include iron (■) and cobalt (■).
, chromium (■), polyvalent metal compounds such as copper (II), peracids, quinones, and nitro compounds are used. Typical bleaching agents include ferricyanide; dichromate; organic complex salts of iron (I) or cobalt (I) such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3 - Use of aminopolycarboxylic acids such as diaminopropanetetraacetic acid, glycol ether diamine tetraacetic acid, or complex salts of citric acid, tartaric acid, malic acid, etc.; persulfates; bromates; permanganates; nitrobenzenes, etc. I can do it. Among these, aminopolycarboxylic acid iron (III) complex salts and persulfates, including ethylenediaminetetraacetic acid iron (I [[) complex salts] are preferred from the viewpoint of rapid processing and prevention of environmental pollution. Furthermore, aminopolycarboxylic acid iron(III) complexes are particularly useful in both bleach and bleach-fix solutions. p of bleaching solutions or bleach-fixing solutions using these aminopolycarboxylic acid iron (III) complex salts.
H is usually 5.5 to 8, but in order to speed up the processing,
It is also possible to process at even lower pH.

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary.

Specific examples of useful bleach accelerators include U.S. Pat.
It is described in the specification of No. 858. Also preferred are the compounds described in US Pat. No. 4,552,834. These bleach accelerators may be added to the photosensitive material. These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for photography.

Examples of the fixing agent include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used, especially ammonium thiosulfate. Most widely used. As the preservative for the bleach-fix solution, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred.

The silver halide photographic material of the present invention is generally subjected to a water washing and/or stabilization process after desilvering treatment. The amount of water used in the washing process depends on the characteristics of the photosensitive material (depending on the material used, such as the coupler), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is
al of the 5ociety of Mo
tion Picture and Te1-e
Vision Engineers Volume 64, P, 24
It can be determined by the method described in B-253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. The problem arises. As a solution to the second problem in processing the color photosensitive material of the present invention,
The method for reducing calcium ions and magnesium ions described in JP-A No. 62-288.838 can be used very effectively. Also, JP-A-57-8,542
Isothiazolone compounds and cyabendazole compounds, chlorine-based disinfectants such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., described in the issue, "Chemistry of antibacterial and fungicidal agents" by Hiroshi Horiguchi, "Microorganisms" edited by Sanitation Technology Society sterilization, sterilization,
It is also possible to use the fungicides described in "Anti-mold Techniques" and "Encyclopedia of Antibacterial and Antifungal Agents" edited by the Japan Antibacterial and Antifungal Society.

The pH of the washing water in the processing of the photosensitive material of the present invention is 4-
9, preferably 5-8. The washing water temperature and washing time can be set variously depending on the characteristics of the photosensitive material, its use, etc., but generally it is 20 seconds to 10 minutes at 15-45°C, preferably 30 seconds to 5 minutes at 25-40°C. A range is selected. Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water. In such stabilization treatment, Japanese Patent Application Laid-open Nos. 57-8.543 and 58-14
, No. 834 and No. 60-220.345 can all be used.

Further, following the water washing treatment, a further stabilization treatment may be carried out, such as a stabilizing bath containing formalin and a surfactant, which is used as a final bath for color photosensitive materials for photography. .

Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow liquid resulting from the water washing and/or replenishment of the stabilizing liquid can also be reused in other processes such as the desilvering process.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing.

The silver halide color light-sensitive material of the present invention may optionally contain various 1-phenyl-3
- Pyrazolidones may be incorporated. Typical compounds are disclosed in, for example, JP-A-56-64,339 and JP-A-57-14.
No. 4,547 and No. 58-115.438.

Various treatment liquids in the present invention are used at 10°C to 50°C. Normally, a temperature of 33°C to 38°C is standard, but higher temperatures can be used to accelerate processing and shorten processing time, or lower temperatures can be used to improve image quality and stability of the processing solution. can be achieved. Further, in order to save silver on the photosensitive material, a treatment using cobalt intensification or hydrogen peroxide intensification as described in West German Patent No. 2.226.770 or US Pat. No. 3,674.499 may be carried out.

Further, the silver halide photographic material of the present invention is disclosed in U.S. Pat.
It can also be applied to the heat-developable photosensitive materials described in Patent No. 59-218443, No. 61-238056, European Patent No. 210.66OA2, and the like.

(Example) Examples will be shown and explained below.

Example 1゜ Average iodine content is 15 mol%, average equivalent sphere diameter is 0.8 μm
Using iodobromide i12 double-twinned grains with a particle diameter variation coefficient of 15% and an average aspect ratio of 5.0 as seed crystals, a controlled double jet method was used under conditions such that the silver potential was 140 mV in an aqueous gelatin solution. Shelling was carried out for 30 minutes. The ratio of the core to the shell was 1:2 in terms of silver content, and the composition of the halogen solution was controlled so that the iodine content of the shell was 0 to 7.5 mol%. (
Prescriptions A-E shown in Table 1) Table 1 During shell formation, reduction sensitization was performed using dimethylamine borane (DMAB) and a thiosulfonic acid compound according to the amounts and methods shown in Table 2.

Table 2 Redispersed at 40'C under conditions of pAg 8.9, p) 16.3.

Each emulsion was then combined with 6XIO per mole of silver halide.
-6 moles of sodium thiosulfate and 2X10@-6 moles of chloroauric acid were used to optimally chemically sensitize emulsions Nos. 1 to 5.

In addition, each emulsion was 3XIO- per mole of silver halide.
Optimal chemical sensitization was achieved by adding 'mol of sodium thiosulfate and 3X10-'mol of selenium sensitizer (compound B-E), 2X10-6 mole of chloroauric acid and 4X10-3 mole of sodium thiocyanate. Emulsion Nα6 to 12
．． 15 and 16 were obtained.

Furthermore, prior to chemical sensitization, a spectral sensitizing dye having the following structural formula was added. The selenium sensitizers used in each emulsion are shown below.

Compound B 9ρ 1) Compound C Compound D 8ρ The emulsion and protective layer were coated in the coating amounts shown in Table 3 on a triacetyl cellulose film support provided with an undercoat layer.

Table 3 (1) Emulsion layer Emulsion... Emulsion shown in Table 4 (silver 1.7X10-2 mol/bo) Coupler (1,5XIO-3 mol/bo) Tricresyl phosphate (1, 10g/bo) ・ Gelatin (2,30g/bo) (2)
Protective layer・2,4-dichlorotriazine-6-hydroxy-
5-1-Ryazine sodium salt (0.08 g/Po) and gelatin (1.80 g/Po) These samples were exposed to light for sensitometry and subjected to the following color development process.

The concentration of the treated sample was measured using a green filter.

The results of the photographic performance obtained are shown in Table 4.

The development process used here was carried out at 38°C under the following conditions.

1. Color development... 2 minutes 45 seconds 2. Drifting
White - 6 minutes 30 seconds 3, wash with water...
・・・ 3 minutes 15 seconds 4・ Fixation ・・・・・・ 6
Minute 30 seconds 5, Wash with water 3 minutes 15 seconds 6,
Stability: 3 minutes and 15 seconds The processing composition used in each step is as follows.

Color developer Sodium nitrilotriacetate 1.4 g Sodium sulfite 4.0 g Sodium carbonate 30.0 g Potassium bromide 1.4 g Hydroxylamine sulfate 2.4 g 4-(N-ethyl-
N-βhydroxyethylamino)-2-methyl-aniline sulfate 4.5g Add water 11 Bleach solution Ammonium bromide 160.0g Aqueous ammonia (28%) 25.0ml
Ethylenediamine-tetraacetic acid sodium salt 130 g Glacial acetic acid 14 ml Add water 11 Fixer Sodium tetrapolyphosphate 2.0 g Sodium sulfite 4.0 g Ammonium thiosulfate (70%) 175.0 m 42 Sodium bisulfite 4.6 g Add water 12 Add 8.0ml of stabilized formalin water 11 Exposure is 1/1
A normal wedge exposure was performed at 00 seconds.

The light source used was one whose color temperature was adjusted to 4800'' using a filter, and a yellow filter was also used.Sensitivity was compared based on fog and optical density of 0.2.

As can be seen from Table 5, the emulsion with a low surface silver iodide content (
If gold, sulfur, or selenium enhancers are added to emulsion A), the capri will increase significantly and the sensitivity cannot be effectively increased. When an emulsion with a high surface silver iodide content (emulsions B-E) is amplified with gold, sulfur, and selenium, fog caused by chemical sensitization can be reduced, making it possible to prepare an emulsion with extremely high sensitivity. Therefore,
When a surface high iodine emulsion is combined with a selenium enhancer, an emulsion with extremely high sensitivity is obtained.

It can be seen that the above effect is more pronounced in emulsions subjected to reduction sensitization during grain formation, and that compounds B and C are preferable to D as selenium sensitizers.

Example 2 To the chemically sensitized emulsion 1.4.6°9 prepared in Example 1, ■ and ■ shown in Table 0 below were added to ■ to prepare a red-sensitive emulsion.

Sample 201, which is a multilayer color light-sensitive material, was prepared by coating layers having the compositions shown below on a cellulose triacetate film support which had been undercoated with these emulsions.

(Photosensitive Layer Composition) The numbers corresponding to each component indicate the coating amount expressed in g/rrr units, and for silver halide, the coating amount of silver II. However, for sensitizing dyes, the coating amount is expressed in moles per mole of silver halide in the same layer.

(Sample 201) 1st layer; antihalation layer black colloidal silver...Silver 0.18
Gelatin...0.40
2nd layer; middle layer 2.5-di-t-pentadecylhydroquinone...0゜1
8EX-1... Q, 07 EX-3... 0.02 EX-12... 0.002 U-1... 0.06 U-2... 0.08 Ll-3...0.10 HBS-1...0.10 HBS-20...0.02 Gelatin...1.04
Third layer (first red-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (silver iodide 6 mol%, average grain size 0)
．． 6μ, coefficient of variation regarding particle size 0.15)...Silver 0.55 Sensitizing dye I...6.9X10-
5 Sensitizing dye ■...1.8XIO
-'Sensitizing dye■...3.1X1
0-' Sensitizing dye ■...4.0X
10-5EX-2...0.350 HBS-1...0.005 EX-10...0.020 Gelatin...1.20
4th layer (second red-sensitive emulsion layer) Tabular silver iodobromide emulsion (silver iodide 10 mol%, average grain size 0.7μ, average aspect ratio 5.5, average thickness 0.2μ
)...Silver 1.0 sensitizing dye■
...5. lX10-5 sensitizing dye■...1.4X10-5 sensitizing dye■...2.3 X 10-'
Sensitizing dye IV 0. -03.0XI
O-5EX-2...0.400 EX-3,...0.050 EX-10...0.015 Gelatin'...1.30 5th layer (3rd red anger Emulsion layer) Silver iodobromide emulsion 1, 4.6 or 9..., silver 1.60
EX-3...0.240 EX-4...0.120 HBS-1...0.22 HBS-2...0.10 Gelatin...1.63
6th layer (intermediate layer) EX-5..., 0.040 HBS-1...0.020 Zera"'...0.8
0 7th layer (first green emulsion layer) Tabular silver iodobromide emulsion (silver iodide 6 mol%, average grain size 0
．． 6μ, average aspect ratio 6.0, average thickness 0.15μ
) ・・・Silver 0.40 sensitizing dye V
...3.0XIO-5 sensitizing dye■ ...1. OX 10-' Sensitizing dye ■...3.8 X 10-
'EX-6... 0.260 EX-1... 0.021 EX-7 days... 0.030 Eχ-8... 0.025 HBS-1... 0.100 HBS-3...00inch0 Gelatin...0.75
8th layer (second green-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (silver iodide 9 mol%, average grain size 0)
．． 7μ, coefficient of variation regarding particle size 0.18)...Silver 0.80 Sensitizing dye V...2. lX10-
'Sensitizing dye■...7.0X10
-'Sensitizing dye ■ ..., 2.6X1
0-'EX-6...0.180 EX-1...0.008 EX-7...0.012 EX-8...0.010 HBS-1... 0.160 HBS-4... 0.008 Gelatin... 1. lO
9th layer (third green-sensitive emulsion layer) Silver iodobromide triple structure (core silver iodide 3 mol%, first coating layer 15 mol%, second coating layer 8 mol%) tabular grains (average grain size 1 .0μ, average aspect ratio 8.0)
...Silver 1.2EX-6...0.
065 EX-11...o, oa.

EX-1...0.025 HBS-1...0.25 HBS-2...0.10 Gelatin 004. 1.74
1st O layer (yellow filter layer) Yellow colloidal silver...Silver 0.05
EX-5...0.08 HBS-3...0.03 Gelatin...0.9
5 Eleventh layer (first blue-sensitive emulsion layer) Tabular silver iodobromide emulsion (silver iodide 6 mol%, average grain size 0)
．． 6μ, average aspect ratio 5.7, average thickness 0.15
)...Silver 0.24 concentrating dye ■...3.0X10-'EX
-9...-0,8S EX-8... 0.12 HBS-1... 0.28 Gelatin... 1.28
12th layer (second blue-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (silver iodide 10 mol%, average grain size 0.8μ, coefficient of variation regarding grain size 0.16)...
Silver 0.45 Sensitizing dye ■ 2. lX10-
'EX-9...0.20 EX-10...0.015 HBS-1...0.03 Gelatin...0.46
13th layer (third blue-sensitive emulsion layer) Silver iodobromide double structure (core silver iodide 35 mol%, shell 2 mol%), average grain size (1.2μ), aspect ratio 3.
0, Emulsion ■...Silver 0.77EX-9.
...Pa 0.20 HBS-1...0.07 Gelatin...0.69
14th layer (first protective layer) Silver iodobromide emulsion (silver iodide 1 mol%, average grain size 0.07
μ) ...Silver 0.50-4
...0.11U-
5... 0.17 HBS-1... 0.90 Gelatin... 1.00
15th layer (second protective layer) Polymethyl acrylate particles (diameter 1.5 am) -・-0,5
43-1...0.15 3-2...0.
05 Gelatin...0.
72 In addition to the above ingredients, each layer contains gelatin hardening agent H-1.
and surfactant were added. The structural formulas of the compounds used are shown in Table 0.

Sample 201 except that the silver iodobromide emulsion in the fifth layer was changed.
Samples 202 to 204 were prepared in the same manner as above.

These samples were exposed to light for sensitometry and subjected to the following color development process.

The concentration of the treated sample was measured using a red filter, a green filter, and a blue filter. The results obtained are shown in Table 5.

The results of photographic performance are expressed as relative sensitivities when the sensitivity of the red-sensitive layer of sample 201 is set to 100.

Processing method Color development processing was carried out at 38°C according to the following processing steps.

Color development 3 minutes 15 seconds Bleached white 6 minutes 30 seconds Water washing 2 minutes 10 seconds Fixed arrival time: 4 minutes 20 seconds Water Wash 3 minutes 15 seconds Safe, stable, 1 minute, 05 seconds The composition of the treatment liquid used in each step is as follows.

Color developer Diethylenetriaminepentaacetic acid 1.0g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0g Sodium sulfite 4.0g Potassium carbonate 30.0g Potassium bromide 1.4g Potassium iodide 1.3 ■Hydroxylamine sulfate 2 .484-(N-ethyl-N-
β-hydroxyethylamino)-2-methylaniline sulfate 4.5g Add water 1.01 pH 10.0 Bleach solution Ethylenediaminetetraacetic acid ferric ammonium salt 100.0g Ethylenediaminetetraacetic acid disodium salt 10.0g Ammonium bromide 150 .0 g ammonium nitrate Add 10.0 g water 1.01 pH 6.0 Fixer Ethylenediaminetetraacetic acid disodium salt 1.0 g Sodium sulfite 4.0 g Ammonium thiosulfate aqueous solution (702) 175.0 m 1 Sodium bisulfite 4.6 g Water In addition, 1.01 pH 6.6 stabilized formalin (40%) 2.0 mj2
Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3g
Add water 1.0! Table 5 As is clear from Table 6, the high sensitivity of the emulsion of the present invention was also confirmed in the color multilayer coating samples.

Table A V-1 H3 V-2 H3 V-3 e Hff V-4 p " H3 IV-5 IV-6 IV-7 ■ CH3 IV-8 P CHl IV-9 e CH.

■-10 CH3 ■-11 " CH.

CH.

IV-13 p " CH3 ■-14 p ■ CH3 ■-15 p CH3 ■-16 p CHl IV-17 ■-18 ■-19 ■-20 H3 ■-21 ■-22 ■-23 ■-24 CH31-fi3 ■-25 CH3CH:1 CH,CH3 ■-26 ■-27 e e e e qρ e Se ■-10 Se ■-11 (Fa ■-12 Se sum p ■-15 Se Se p ■-19 ■-20 sum ■-22 ■-23 p ■-25 Sp ■-26 sum HI ■-27 Tsutomu ■-28 Q.

■-29 qρ ■-30 ■-32 ■-33 ■-34 qρ ■-35 Q.

■-36 Ku p ■-37 qρ ■-38 Sp ■-39 e ■-40 p ■-43 籟■-45 e Table 8 (1-1) CH35O! 5Na (1-2) C,H5SO,5Na (1-3) C,H,SO□5K (14) C4H95O*S L t (1-5) CbH,5SO2SNa (1-6) Cs1(+tSOzSNa(1B) C0
HszSOzSNa (19) CtzHzsSOzSNa (110) C0HszSOzSNa (1-12) t-CH35O! 5Na(1-13)
CH,0CHzCH,5OzS-Na(115)CHz
=CHCHzSO2SNa to KSSO□(CHz)zS o,s KN a S S
O, (CHz), 5OzS N aN a S S
O! (CHz), S (CHz), S O, S N a
(2-1) C, H, So□5-CH:l (22)
Ca HI 7 S Oz S CHz CH3
(25) C2H55O□S CHz CHz CN
CH.

C,H9S O□5CHCH,CN C,H%5OzS CH,CH2CHzc HgoHC
HsS S Ch(CHz)4S OzS CHsCH
zS S 0x(CHz)zS OzS CHsCJs
SOzSCHgCFlzSO□CH, CH25SO□C
zHsC, H3S025 S SO□Cz H5(n)
C:1H7S02S S 5OzC3Ht(n) Table 0 H EX-1 C! EX-2 0M EX-3 SLlsNa S1υ, NaX-4 H Country Yosokubacterium
Sumasa Hz X-11 3-I S-2■ zHs zHs

Claims (6)

[Claims] (1) A silver halide emulsion layer containing silver halide grains that has been selenium sensitized in any step of emulsion production and contains 5 mol% or more of silver iodide on the surface of the silver halide grains,
A silver halide photographic material having at least one layer on a support. (2) The silver halide photographic material according to claim (1), which is subjected to reduction sensitization during grain growth. (3) The claim (
2) The silver halide photographic material described above. [I] R-SO_2S-M [II] R-SO_2S-R^1 [III] RSO_2S-Lm-SSO_2-R^2 In the formula, R, R^1, and R^2 may be the same or different, It represents an aliphatic group, an aromatic group, or a heterocyclic group, and M represents a cation. L represents a divalent linking group, and m is 0 or 1. The compounds of general formulas [I] to [III] may be polymers containing divalent groups derived from the structures represented by [I] to [III] as repeating units. Further, when possible, R, R^1, R^2, and L may be bonded to each other to form a ring. (4) Claims (1) and (2) characterized in that the sensitization is carried out in the presence of a selenium sensitizer represented by the general formula [IV].
) or the photographic material described in (3). General formula [IV] In the formula, R_1, R_2, R_3, and R_4 are an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a heterocyclic group, an acyl group, a carboxy group, an alkoxycarbonyl group, and an aryloxy group. Represents a carbonyl group, carbamoyl group, or sulfamoyl group. However, tetramethylselenourea is excluded. (5) The silver halide photographic material according to claim (4), wherein the general formula [IV] is represented by the following general formula [V]. General formula [V] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_5, R_6, R_7, and E are alkyl groups,
Represents a cycloalkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, heterocyclic group, acyl group, carboxy group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, and sulfamoyl group. However, E is a group having a Hammett's substituent constant σp value of −0.1 or more. (6) Claims (1) and (2) characterized in that the sensitization is carried out in the presence of a selenium sensitizer represented by the general formula [VI].
) or the photographic material described in (3). General formula [VI] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_8, R_9, R_1_0, R_1_1 are hydrogen atoms, alkyl groups, cycloalkyl groups, alkenyl groups,
Alkynyl group, aralkyl group, aryl group, heterocyclic group, acyl group, carboxy group, alkoxycarbonyl group,
Represents an aryloxycarbonyl group, a carbamoyl group, or a sulfamoyl group. However, R_8, R_9, R_9
and R_1_0, R_1_0 and R_1_1, and R_1_1 and R_8 are combined with each other to form a ring.