JPH04184331A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain an emulsion having high sensitivity and improved granulari ty by incorporating normal crystalline particles sensitized with selenium in a compd. expressed by formula I or II into at least one layer of a silver halide photographic sensitive material. CONSTITUTION:The use amt. of the selenium sensitizer expressed by formulae I and II depends on the selenium compd. to be used, silver halide particles, chemical aging conditions, etc. However, generally about 10<-8>-10<-4>mol of the sensitizer is used to 1mol of the silver halide. The silver halide particles are normal crystals having an octahedral or tetradecahedral shape, and substantially consists of silver iodide/boride having a part of different silver iodide content in one particle.

Description

[Detailed description of the invention] (Industrial application field) The present invention relates to a silver halide photographic material.

In particular, the present invention relates to a silver halide photographic material using a silver halide emulsion which has improved fog and sensitivity, improved graininess, and improved pressure desensitization.

(Prior art) In the photographic industry, various studies have been carried out to improve sensitivity, image quality, pressure resistance, and storage durability. When you think about it, it cannot be said that the level is sufficient and further improvement is essential.

In order to meet the demands for higher sensitivity and higher image quality, it is necessary to increase the sensitivity of emulsion grains, and various attempts have been made in this regard.

One of these is the study of chemical sensitization methods, and representative methods include sulfur sensitization, selenium sensitization, noble metal sensitization such as gold, reduction sensitization, and various sensitization methods using combinations of these methods. It is being

Among these methods, the selenium sensitization method has a greater sensitizing effect than the commonly used sulfur sensitization method, but tends to cause greater fogging and to tend to be softer.

Regarding this problem, it was found in Japanese Patent Application No. 2-130976 that sensitivity can be increased while suppressing increase in fog by chemically sensitizing using a specific selenium compound. However, in our study, there was a problem that tabular grains such as those described in Examples of Japanese Patent Application No. 2-130976 deteriorated in grain shape due to selenium sensitization.

Regarding selenium sensitization of normal crystals, see JP-A-58
-126526, 59-180536, 59-18
1337, 59-185329, 59-18533
0, No. 59-187338, No. 59-192241, etc., but it cannot be said that increased sensitivity is achieved while suppressing the increase in fog to a satisfactory level.

On the other hand, it is known that it is effective to have parts with different halogen compositions inside the particles in order to achieve higher sensitivity and higher image quality using normal crystals.
-154232, 59-177535, 60-13
8538, 60-254032, 61-24515
An example can be seen in 1.

However, the performance of the emulsion grains obtained by the methods described in these publications is at a level that requires further improvement in response to today's increasingly sophisticated demands for higher sensitivity and higher image quality. Additionally, in general, photosensitive materials using emulsions consisting of normal crystals that have internal portions with different halogen compositions suffer from a large amount of so-called pressure desensitization, in which the density decreases in areas where pressure is applied.
Countermeasures are desired.

(Problems to be Solved by the Invention) We attempted to provide an emulsion with improved graininess while having high sensitivity by reducing the deterioration in graininess caused by selenium sensitization.

In addition, we have found an effect that we could not have expected at first, namely, improved pressure desensitization of normal crystal grains that have internal portions with different halogen compositions.

Based on the above results, it is an object of the present invention to provide a silver halide photoluminescent material with high sensitivity and excellent graininess. Another object of the present invention is to provide a silver halide photosensitive material that exhibits less reduction in sensitivity due to folding.

(Means for solving problems) The above objects of the present invention are achieved by the following configuration.

That is, a small amount of the following compound (I) or (1) is added to the layer.
This is achieved by a silver halide photographic material characterized by containing normal crystal grains sensitized with selenium with at least one compound represented by:

General formula (1) % formula % In the formula, R,, R,, R3, 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, Represents an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, or a sulfamoyl group.

(However, R, to R1 are not all methyl groups) General formula (1) %Formula% In the formula, Rs, Rq, Rq. , 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, a carboxy group, a formyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, represents a sulfamoyl group (provided that R1 and R9, Rq
and Ro. , at least one of RI6 and R11, Ro and R1
The sets are assumed to be combined with each other to form a ring. ) Next, general formula (1) will be explained in detail.

In the formula, R,, R,, R,, R4 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 11 (e.g. propargyl, 3-pentynyl)
, substituted or unsubstituted 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), a substituted or unsubstituted carbamoyl group (eg, carbamoyl, dimethylcarbamoyl, propylcarbamoyl), or a substituted or unsubstituted sulfamoyl group (eg, sulfamoyl, N-methylsulfamoyl).

Here, examples of substituents for R1, Rz, Rs, and R1 include the following. These groups may be further substituted.

That is, alkyl groups (e.g. methyl, ethyl, butyl), cycloalkyl groups (e.g. cyclopentyl, cyclohexyl), alkenyl groups (e.g. furyl, 3-pentenyl), alkynyl groups (e.g. propargyl, 3-pentynyl), aralkyl groups (e.g. propargyl, 3-pentynyl), (e.g. benzyl, phenethyl), aryol groups (e.g. phenyl, naphthyl), heterocyclic groups (e.g. pyridyl, thienyl, furyl, imidazolyl, piperidyl, morpholyl, benztriazolyl, benzoxacylyl, thiazolyl, tetrazolyl, tetraaza) indenyl, 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 group, dimethylamino, ethylamino), ammonio group (e.g. trinotylammonio), acylamino group (e.g. acetylamino, benzoylamino), carbamoyl group (e.g. carbamoyl, dimethylcarbamoyl, propylcarbamoyl), sulfonylamino group (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. methylsulfinyl, ethylsulfinyl), sulfo groups, sulfino groups, hydroxy groups, halogen groups (e.g. fluoro, chloro, bromo), cyano basis,
These include a nitro group, a ureido group (eg, ureido, N'-methylureido), a phosphono group, and a mercapto group.

Among the compounds represented by the general formula (I), the following general formula (II) is preferably mentioned.

General formula (n) e R, R In the formula, Rs, R,, R, and E 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, and a carboxy group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, or sulfamoyl group (provided that E is a group having a Hammett's substituent constant σρ value of −0.1 or more).

Next, general formula (II) will be explained in detail.

In the formula, R,, R,, R, are R+, R in general formula (1)
It has the same meaning as z, Rs, and R4.

E is Hammett's substituent constant, σp value (Journal
Op Medicinal Chemistry” (Journal
of Medicinal Chemistry) Vol. 16, p. 304 (1973), Vol. 20, p. 304 (1973)
(1977). ) is -0°1 or more, a substituted or unsubstituted alkyl group (e.g. chloromethyl, trifluoromethyl group, acetonyl),
Substituted or unsubstituted cycloalkyl groups (e.g. cyclopentyl), substituted or unsubstituted alkenyl groups (e.g. 1-chloro-3-butenyl, l-chloro-4-octenyl), substituted or unsubstituted alkynyl groups (e.g. l
-chloro-3-7"thinyl, 1-chloro-4-octenyl), substituted or unsubstituted aralkyl groups (e.g. benzyl), substituted or unsubstituted aryl groups (e.g. phenyl, pentafluorophenyl), 1fllk moly or Unsubstituted heterocyclic groups (e.g. 4-pyridyl, 2-benzoxasilyl, l-ethyl-2-benzimidazolyl), substituted or unsubstituted acyl groups (e.g. acetyl,
formyl, benzoyl, pivaloyl), carboxy group,
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), Represents a substituted or unsubstituted sulfamoyl group (eg, sulfamoyl, methylsulfamoyl).

In general formula (n), preferred embodiments are shown below.

R+, Rz, Rs represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted acyl group, E is a Hammett substituent A substituted or unsubstituted heterocyclic group, a substituted or unsubstituted acyl group, a substituted or unsubstituted carbamoyl group, a substituted alkyl group, a substituted aryl group having a constant σρ value of 0.3 to 0.9. preferable.

More preferably, R,, R,, R, is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group,
E representing a substituted or unsubstituted acyl group is more preferably an acyl group having a Hammett's one-substitution constant σρ value of 0.5 to 0.8.

Next, general formula (1) will be explained in detail.

In the formula, R,,R,,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, 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 (eg phenoxycarbonyl), substituted or unsubstituted carbamoyl group (eg carbamoyl, dimethylcarbamoyl, propylcarbamoyl), substituted or unsubstituted sulfamoyl group (eg sulfamoyl, methylsulfamoyl).

At this time, the group that is combined to form a ring is a substituted or unsubstituted alkylene group (which may include an ether, a thioether, a substituted or unsubstituted amino group, etc., such as methylene, ethylene, propylene, butylene, hexylene, 1-Methylethylene, -CHxCToOCIt
zCHz-, -CHzCHtNHCHzCHz-), substituted or unsubstituted aralkylene groups (e.g. benzylidene), substituted or unsubstituted arylene groups (e.g. phenylene, naphthylene), substituted or unsubstituted heterocyclic linking groups (e.g. or Examples of substituents for the combined linking group (for example, Re, R9, Rho, and Ro here include those mentioned for Rt, Rt, Rs, and R4 in general formula (I)).

In the general formula (III), preferably the ring formed by R1 and R9, R1 and R3°, R1, and R11, R11 and R1 is a 4- to 7-membered ring *Rs, Rq, R1°,
R11 is preferably a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted acyl group, or a substituted or unsubstituted carbamoyl group.

In general formula (III), more preferably R, and R9, R
1 and R1°, R111 and R11% The ring formed by R11 and R8 is a 5- or 6-membered ring, and R1, R9, R
1°, R8 is a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted acyl group.

Specific examples of the compounds of the present invention are shown in Table A at the end, but the compounds of the present invention are not limited thereto.

The compounds represented by general formulas (1) and (I[[) can be synthesized according to known methods. That is, 5aul
Pataiii, rThe chemistry of organic selenium and tellurium compounder J
rganic 5ele-nius and tell
urium compounds) Volume 2, page 255~
It can be synthesized according to the method described on page 258 (1987).

Next, the methods for synthesizing the compounds of general formulas (, 1) and (11) will be explained by giving typical synthesis examples.

Synthesis Example 1 Synthesis of Compound 1-1 1-(1) Synthesis of N-acetyl-N,N',N'-trimethylthiourea Add 37g of acetic anhydride to 400jd of a toluene solution of 740g of N,N,N'-1 trimethylthiourea. was added, and then 0.5 d of concentrated sulfuric acid was added while stirring. The reaction solution was heated to 80°.
After stirring for 6 hours, the mixture was cooled to room temperature. After adding 400 m of water to this for extraction, salt was added to the aqueous layer to prepare 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 1-(III) N-acetyl-N,N',N'
-42g of trimethylthiourea and 90g of iodomethane
and stirred at room temperature for 8 hours. The generated crystals were collected by filtration and washed with chloroform to obtain the desired product. Yield 2
3g 1-(3) Synthesis of Compound I-1 2.0g of selenium was added to 150d of dry ethanol under a nitrogen atmosphere, and after cooling to 0°C, 1.0g 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 NaH3e.
After obtaining the solution, add N-acetyl-N,N' to this solution.
, N', S-tetramethylthiouronium iodide4.
50 d of 0 g of ethanol solution was added and left at room temperature for 20 hours. Add glacial acetic acid to make it slightly acidic, then reduce to 70M under reduced pressure.
It was concentrated to 1.

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 and hexane (15M, 1.10d each) to obtain 3 g of the desired exemplary compound (1)-12.

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 ■-29 2-(1) Synthesis of N,N'-dimethylethylenethiouronium iodide A solution of 20 g of N,N'-dimethylethylenethiourea in acetone 30 g of iodomethane was added to the mixture, and the mixture was 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 ■-29 From 4.0 g of N,N'-dimethylethylenethiouronium iodide obtained in 2-(III), the desired example was prepared in the same manner as in Synthesis Example 1. 2.0 g of Compound 1[[-29 was obtained. Nuclear magnetic resonance spectrum, mass spectrum,
Elemental analysis was 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 (1) and (III) are used as selenium sensitizers.Therefore, it is difficult to predict the sensitizing effect, fogging, and other photographic effects caused by these compounds. Although it was extremely difficult,
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 -
'' to 10-4 mol, preferably about 10-7 to 10-5 mol.

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

In the present invention, it is preferable to use noble metal sensitizers 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, silver sulfide, gold selenide, etc. '-? As much as 10-'' moles can be used.

In the present invention, it is also preferable to use a sulfur sensitizer in combination. Specifically, thiosulfates (e.g. hypo),
Known unstable sulfur compounds such as thioureas (e.g. diphenylthiourea, triethylthiourea, allylthiourea) and rhodanines can be used, and about 10-7 to 104 moles can be used per mole of silver halide. .

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. In particular, among these, thiocyanates, thioether compounds, tetrasubstituted thiourea compounds and 1,000-ion compounds can be preferably used. The amount used can be approximately 10<-5> to 5*10<-2> mol per 1 mol of silver halide.

In the present invention, selenium sensitization can also be carried out in the presence of a nitrogen-containing heterocyclic compound that forms a complex with silver, as described in JP-A-58-126526.

In this case, the nitrogen-containing heterocyclic compound is preferably an azaindene compound.

Selenium can also be exacerbated in the presence of sensitizing dyes.

The silver halide grains used in the present invention are normal crystals.

Normal crystals include a cube consisting of (100) planes and a (111
) planes, and dodecahedral particles consisting of (110) planes disclosed in Japanese Patent Publication No. 55-42737 and Japanese Patent Application Laid-Open No. 60-222842 can be used. Further J
Our own of Imaging 5science
As reported in Vol. 30, p. 247 (1986), (211) is a representative example of (hl) Menko, (3
The (hhl) surface roughened surface represented by 31), the (hkO) surface roughened surface represented by the (210) surface, and the (hkl) surface roughened surface represented by the (321) surface also require some ingenuity in the preparation method. It can be selected and used depending on the purpose.

Tedecahedral particles in which (100) and (i 11) planes exist in one particle, particles in which (100) and (110) planes coexist, or particles in which (111) and (110) planes coexist, etc. Particles having two surfaces or a large number of surfaces coexisting can also be selected and used depending on the purpose.

The silver halide grains used in the present invention are preferably normal crystal grains whose outer surfaces have an octahedral or tetradecahedral shape.

For the normal crystal grains of the present invention, only one type of emulsion can be used in a photosensitive silver halide emulsion layer, and if necessary,
It is also possible to use a mixture of two or more emulsions. It is also possible to mix and use emulsions other than those of the present invention in an amount of less than 50% by weight of silver halide.

The normal crystal silver halide grains of the present invention preferably have internal portions with different halogen compositions.

Typical examples are, for example, Japanese Patent Publication No. 43-13162, Japanese Patent Application Publication No. 61-215540, and Japanese Patent Application Publication No. 60-2228.
No. 45, JP-A-60-143331, JP-A-61-7
These are core-shell type or double-structured particles, as disclosed in No. 5337, in which the interior and surface layers of the particles have different halogen compositions. In addition, instead of a simple double structure, it is possible to have a triple structure as disclosed in JP-A-60-222844, or a multilayer structure with more than that, or to have a core-shell double structure with different compositions on the surface. It is possible to apply a thin layer of silver halide.

In order to give a structure to the inside of a particle, it is not only possible to create a structure that envelops it as described above (it is also possible to create a particle that has a so-called bonding structure.
No. 0, JP-A-58-108526, European Patent No. 199
．． 29OA2, JP-B No. 58-24772, JP-A-5
No. 9-16254 and the like. The crystal to be joined can have a composition different from that of the host crystal and can be formed in a state where it is joined to an edge, part of a corner, or a surface of the host crystal. Such a bonded crystal can be formed even if the host crystal is uniform in halogen composition or has a core-shell structure.

In the case of a bonded structure, it is naturally possible to combine silver halides, but it is also possible to create a bonded structure in which silver halide is combined with a silver salt compound that does not have a rock salt structure, such as silver rhodan or silver carbonate. .

Furthermore, non-silver salt compounds such as lead oxide may also be used if a bonded structure is possible.

The silver halide grains to be selenium sensitized in the present invention include silver bromide,
Silver iodide, silver iodobromide, silver chlorobromide, silver chloroiodide, silver chloride, silver chloroiodobromide may be used, but those consisting essentially of silver iodobromide are preferable. Containing silver bromide means that the ratio of iodine and bromine to the halogens in the entire emulsion grain is 9.
0% or more.

The silver halide grains used in the present invention preferably consist essentially of silver iodobromide, and each grain preferably has portions with different silver iodide contents.

In the case of grains having portions with different silver iodide contents within one grain, they can have a double structure, a triple structure or more. In that case, the silver iodide content inside the grains can be made higher or lower than the silver iodide content on the grain surfaces.

When grains having different silver iodide contents within one grain are formed by bonded crystals, the silver iodide content of the bonded crystal may be lower than the silver iodide content of the host crystal. It can also be made higher.

The normal crystal grains used in the present invention preferably have a portion within the grains with a silver iodide content that is 5 mol% or more higher than the average silver iodide content on the grain surface.

The average silver iodide content on the grain surface is preferably 10 mol% or less.

The silver iodide content of the high silver iodide content portion is preferably 10 mol % or more higher than the silver iodide content of the surface.

The high silver iodide content portion is preferably made of silver iodobromide having a silver iodide content of 35 mol % or more and 40 mol % or less, or pure silver iodide.

The high silver iodide content portion may be unevenly distributed anywhere within the silver halide grain, for example, it may be present in the central region of a double structure grain, or it may be present in any part other than the outermost layer of a triple structure or more multiple structure. It may exist as any layer within the normal crystal grain, or it may be unevenly distributed in the region near the apex of the outer surface within the normal crystal grain, or conversely, it may be unevenly distributed in the area near the apex where it does not exist. .

In a multilayer structure with a double structure or more, the particle shape after forming each layer constituting the multilayer structure may be octahedral, tetradecahedral, or cubic (and each layer may have a different shape. For example, low iodine 14 It is possible to take the form of a triple structure in which the outside of the face piece is coated with a high iodine layer to form an octahedron, and the outside is further coated with a low iodine layer to finally form a tetradecahedron.

The boundaries between parts of different compositions may be clear boundaries or indefinite boundaries. Furthermore, a preferable nti is one in which the composition is positively and continuously changed.

In the case of silver halide grains in which two or more silver halides exist as crystals or in a structure, it is important to control the halogen composition distribution between grains. Kaisho 60-254
It is a desirable characteristic that the halogen distribution among the zero particles described in No. 032 is uniform. Especially the coefficient of variation 20
An emulsion having a high uniformity of less than % is preferable. Another preferable form is an emulsion in which there is a correlation between grain size and halogen composition.

For example, there may be a correlation such that large-sized particles have a high iodine content and small-sized particles have a low iodine content. Depending on the purpose, a reverse correlation or a correlation with other halogen compositions can be selected. For this purpose, it is preferable to mix two or more emulsions having different compositions.

It is important to control the halogen composition near the surface of the particles. Increasing the silver iodide content or silver chloride content in the vicinity of the surface changes dye adsorption properties and development speed, and can be selected depending on the purpose. When changing the halogen composition near the surface, it is possible to choose either a structure that envelops the entire particle or a structure in which it is attached only to a portion of the particle. For example, when changing the halogen composition of only one side of a tetradecahedral grain consisting of (100) and (111) planes, or when changing the halogen composition of one of the main plane and side surface of a tabular grain.

The silver halide emulsion used in the present invention is subjected to a treatment for rounding grains as disclosed in European Patent No. 96.727B1, European Patent No. 64,412B1, etc., or West German Patent No. 2.306.447C2. , JP-A-60-2
Surface modification as disclosed in No. 21320 may also be performed.

Although particles generally have a flat structure, it is preferable in some cases to intentionally form irregularities.

JP-A-58-106532, JP-A-60-22132
The method of drilling a hole in a portion of a crystal, such as the center of a vertex or face, as described in U.S. Pat.
An example is the ruffled particles described in No. 643,966.

The grain size of the emulsion used in the present invention is evaluated by the circular equivalent diameter of the projected area using an electron microscope, the spherical equivalent diameter of the grain volume calculated from the projected area and grain thickness, or the spherical equivalent diameter of the volume by the Coulter counter method. can. In the present invention, particles ranging from ultrafine particles having an equivalent sphere diameter of 0.05 microns or less to coarse particles exceeding 10 microns can be used. Preferably, grains of 0.1 micron or more and 3 microns or less are used as photosensitive silver halide grains.

The emulsion used in the present invention may be a so-called polydisperse emulsion with a wide grain size distribution or a monodisperse emulsion with a narrow size distribution, depending on the purpose. As a measure representing the size distribution, the coefficient of variation of the circular equivalent diameter of the projected area of particles or the equivalent sphere diameter of volume may be used. When using a monodisperse emulsion, it is preferable to use an emulsion with a size distribution in which the coefficient of variation is 25% or less, more preferably 20% or less, even more preferably 15% or less.

In the case of normal crystals, dislocation lines can be observed with an electron microscope if the size is such that electron beams can pass through them.

For silver halide grains larger than this size, observation of dislocation lines is possible by reducing the thickness of the silver halide grains using a suitable solvent to the extent that electron beams can pass through them. It is preferable to select particles that do not contain any dislocation lines, particles that contain several dislocation lines, or particles that contain many dislocation lines depending on the purpose. Dislocation lines should be introduced near the apex of the particle or at specific parts such as edges. It is preferable to limit it to .

The emulsion used in the present invention can be prepared using the so-called Chondrold double jet method. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

A method of adding precipitated silver halide grains to a reaction vessel for emulsion preparation (for example, US Pat. No. 4,3
34.012, 4,301,241, 4.15
No. 0,994) are preferred in some cases, and these can be used as seed crystals, and are also effective when supplied as silver halide for growth. In the latter case, it is preferable to add an emulsion with a small grain size, and the addition method can be such as adding the entire amount at once, adding in multiple portions, or adding continuously. In some cases, it is also effective to add particles of various halogen compositions to modify the surface.

Methods for converting most or a small portion of the halogen composition of silver halide grains by a halogen conversion method are described in U.S. Pat. No. 3,477.852, U.S. Pat. No. 430, West German Published Patent Application No. 3.819.241, etc., and is an effective particle forming method. Solutions of soluble halogens or silver halide particles can be added to convert to more difficult to tolerate silver salts. At that time, you can choose a method such as converting to -degrees, converting by dividing into multiple times, or converting continuously.

In addition to the method of adding soluble silver salts and halogen salts at a constant concentration and constant flow rate during grain growth, British Patent No. L46
No. 9,480, U.S. Patent No. 3,650,757, U.S. Patent No. 4
, 242,445, particle formation methods that involve varying concentrations or varying flow rates are preferred methods. By increasing the concentration or increasing the flow rate, the amount of silver halide supplied can be varied as a linear, quadratic, or more complex function of addition time.

It is also preferable to reduce the amount of silver halide supplied, if necessary. Furthermore, when adding multiple soluble silver salt solutions with different compositions or adding multiple soluble halogen salt solutions with different compositions, an addition method in which one is increased and the other is decreased is also an effective method. be.

As a mixer for reacting a solution of a soluble silver salt and a soluble halogen salt, U.S. Pat.
．． No. 785.777, West German Published Patent No. 2.556.885
2.555.364 can be appropriately selected and used.

Silver halide solvents are useful for promoting ripening. For example, it is known to have an excess of halide ions present in the reactor to promote ripening. Other ripening agents can also be used. These ripening agents are
The entire amount can be blended into the dispersion medium in the reactor before adding the silver and halide salt, or it can be introduced into the reactor at the same time as the halide salt, silver salt, or peptizer is added. can. Another variant! As S-like, the ripening agent can also be introduced independently at the halide salt and silver salt addition steps.

As a ripening agent, ammonia, thiocyanate (e.g.
U.S. Pat. No. 3,574.628, U.S. Pat. No. 3,021,215, U.S. Pat.
, No. 038,805, No. 4,276.374, No. 4,
No. 297,439, No. 3,704.130, No. 4,7
82,013, JP-A-57-104926, etc.), thione compounds (e.g., JP-A-53-8
No. 2408, No. 55-77737, U.S. Patent No. 4,2
21,863, compounds described in JP-A-53-144319), and silver halide grains described in JP-A-57-202531. mercapto compound,
Examples include amine compounds (for example, JP-A-54-100717).

Gelatin is advantageously used as the protective colloid used in preparing the emulsions of the invention and as a binder for other hydrophilic colloid layers, 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 esters; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol , polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc., single or copolymers thereof. I can do it.

Gelatin includes lime-processed gelatin, acid-processed gelatin, Bull, Soc, Set, Photo,
Japan.

N[Li2. Oxygen-treated gelatin as described in P2O (1966) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used.

The emulsion of the present invention is preferably washed with water for desalination to form a freshly prepared protective colloid dispersion.

The temperature of washing can be selected depending on the purpose, but it is 5″~50°C.
The pH at the time of washing with water can also be selected depending on the purpose, but it is preferably selected between 2 and 10, and more preferably between 3 and 8.

PAg during washing with water can be selected depending on the purpose, but it is preferably selected between 5 and 10. The washing method can be appropriately selected from the noodle washing method, the dialysis method using a semipermeable membrane, the stretching separation method, the coagulation sedimentation method, and the ion exchange method. Coagulation-sedimentation methods include methods using sulfates, methods using organic solvents, methods using water-soluble polymers, methods using gelatin derivatives, and any of these methods can be selected.

When preparing the emulsion of the present invention (for example, during grain formation, desalting process, chemical sensitization, and before coating), it is preferable to have a metal ion salt present depending on the purpose.When doping zero grains, it is preferable to form grains. When used as a particle surface modification or chemical aggravating agent, it is preferably added after particle formation or before the end of chemical sensitization. In addition to doping the entire grain, it is also possible to dope only a part of the core, only the shell, only the epitaxial part, or only the base grain. Metals used for this purpose include Mg, Ca, Sr, Ba5Aj! , Sc, Y, La
, Cr, Mn, Fe, Co, Ni.

Cu, ZnS'Ga, Ru, Rh, Pd, Re.

Os, Ir, Pt, Au5Cd, Hg, Tll.

In, Sn, Pb, Bi, etc. can be used. These metals can be added as long as they are in the form of salts that can be dissolved during particle formation, such as ammonium salts, acetates, nitrates, sulfates, phosphates, hydroxides, 6-coordination complex salts, 4-coordination complex salts, etc. For example, CdB rz , CdC1z , C
d (NOx)2, Pb (NOs L, Pb (
CH3C00)t.

K3 (F e (CN) h), (NH,), CF
e(CN)b ), Ks IrCC1(NH4)3R
tjCj! i, Ka Ru (CN)h.

Ligands for coordination compounds include halo, ako, cyano, cyanate, thiocyanate, nitrosyl, thionitrosyl,
You can choose from oxo and carbonyl. Only one type of these metal compounds may be used, but two or three or more types may be used in combination.

It is preferable to add the above-mentioned metal compound dissolved in water or an appropriate solvent such as methanol or acetone. In order to stabilize the solution, an aqueous hydrogen halide solution (eg HCj!) is added.
, HBr, etc.) or alkali halides (e.g. KC
f, NaCl, KBr.

A method of adding NaBr, etc.) can also be used.

In addition, acids, alkalis, etc. may be added if necessary. The metal compound may be added to the reaction vessel before particle formation, or may be added during particle formation. Further, it can be added to a water-soluble silver salt (eg, A g N O 3 ) or an aqueous alkali halide solution (eg, Na Cl, KBr, KI), and added continuously during the formation of silver halide grains. Furthermore, a solution independent of the water-soluble silver salt and the alkali halide may be prepared and added continuously at appropriate times during grain formation, and it is also preferable to combine various methods of addition.

Addition of chalcogenide compounds during emulsion preparation, such as those described in US Pat. No. 3,772.031, may also be useful. S, S e % In addition to T e, a cyanide salt, a thiocyanate, a selenocyanate, a carbonate, a phosphate, and an acetate may be present.

It is preferable to subject the silver halide emulsion of the present invention to reduction enhancement during, after grain formation and before or during chemical sensitization, or after chemical sensitization.

The reduction enhancement here includes a method of adding a reduction enhancement agent to the silver halide emulsion, a method of adding a reduction enhancement agent to the silver halide emulsion, and a method of adding a reduction enhancement agent to the silver halide emulsion.
Growth or aging method in Ag atmosphere, high pH
It is possible to choose either a method of growing or aging in a high pH atmosphere of pH 8 to 11 called P formation. 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 aggravation can be finely adjusted.

As reduction aggravating agents, stannous salts, ascorbic acid and its derivatives, amines and polyamines, hydrazine derivatives, formamidine sulfinic acid, silane compounds, borane compounds, etc. are known.

For reduction sensitization in the present invention, these known reduction aggravating agents can be appropriately selected and used, and two or more kinds of compounds can also be used in combination. Preferred compounds as reduction sensitizers are stannous chloride, thiourea dioxide, dimethylamine borane, ascorbic acid and its derivatives. The amount of the reduction sensitizer added depends on the emulsion manufacturing conditions, so it is necessary to select the amount added depending on the conditions, but it is suitably in the range of 10@-7 to 10@-3 mol per mol of silver halide.

The reduction sensitizer is added during particle growth in a state dissolved in water or a solvent such as alcohols, glycols, ketones, esters, or amides. 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 reduction sensitizer solution in several portions or continuously over a long period of time depending on the grain growth.

It is preferred to use an oxidizing agent for silver during the manufacturing process of the emulsions of the present invention. An oxidizing agent for silver refers to a compound that acts on metallic silver to convert it into silver ions. Particularly effective are metal oxides that convert extremely minute silver atoms produced as by-products during the process of forming silver halide grains and the process of chemical sensitization into silver ions. The silver ions generated here may form silver salts that are poorly soluble in water, such as silver halide, silver sulfide, and silver selenide, or silver salts that are easily soluble in water, such as silver nitrate. Good too. The oxidizing agent for silver may be inorganic or organic. As an inorganic oxidizing agent,
Ozone, hydrogen peroxide and their adducts (e.g. NaB
O, ・HzO, -3HzO32Naz Co; ・3H
z○,,Na,P,O,・2HzOz,2Na2So
4' H, Oz' 2HzO), Hert Ki', yfa
Salt (eg. Kg S zo s, K z C! Ob,
K! Pt os ), peroxy complex compounds (e.g., Kz (Ti(O□)CzOn) ・3H,O
14, SO, ・Ti(Oz) OH-3O4・2H
20, Nas [VO(0,)(C,H4)!・6
Hz O), permanganate (e.g. KMnO,),
Oxygen salts such as chromates (e.g. Kg Crt O?), elemental halogens such as iodine and bromine, perhalates (e.g. potassium periodate), salts of high valent metals (
Examples include potassium hexacyanoferric acid) and thiosulfonate.

Examples of organic oxidizing agents include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogens (e.g., N-bromsuccinimide, chloramine T1, chloramine B). is given as an example.

Preferred oxidizing agents of the present invention are ozone, hydrogen peroxide and its adducts, halogen elements, inorganic oxidizing agents such as thiosulfonic acid salts, and organic oxidizing agents such as quinones. It is preferable to use the above-mentioned reduction sensitization and an oxidizing agent for silver in combination. A method in which an oxidizing agent is used and then reduction sensitization is performed, a method in which the oxidizing agent is used and then reduction sensitization, a method in which the method is reversed, or a method in which both are allowed to coexist at the same time can be appropriately selected and used. These methods can be used in both the particle formation process and the chemical sensitization process.

The photographic emulsion used in the present invention can contain various 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, such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles,
Mercaptobenzothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, henctriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadorinthione; azaindenes such as triazaindenes, tetraazaindenes (particularly 4-hydroxy-substituted (1,3,3a,7)tetraazaindenes), pentaazaindenes, etc. A number of compounds known as antifoggants or stabilizers can be added. For example, U.S. Patent No. 3,954.
No. 474, No. 3,982,947, Special Publication No. 52-28
660 can be used. One of the preferred compounds is the compound described in JP-A-63-212932. Antifoggants and stabilizers are used at various times before particle formation, during particle formation, after particle formation, during the water washing process, during dispersion after washing, before chemical sensitization, during chemical sensitization, after chemical sensitization, and before coating. It can be added depending on the purpose. In addition to exerting the original antifogging and stabilizing effects when added during emulsion preparation, it can also be used to control crystal walls of grains, reduce grain size, reduce solubility of grains, and control chemical sensitization. It can be used for many purposes, such as controlling the arrangement of dyes.

The photographic emulsion used in the present invention is preferably spectrally sensitized with methine dyes or the like in order to exhibit 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 as a basic heterocyclic nucleus can be applied to these dyes. Namely, viroline nucleus, oxazoline nucleus, thiozoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus, i.e., an indolenine nucleus, a benzindolenine nucleus, an indole nucleus,
A benzoxazole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus, etc. are applicable. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, and a 2-thioxazolidine-2 nucleus having a ketomethylene structure.
, 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiobarbic acid nucleus, and the like can be applied.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.

Representative examples are U.S. Patent No. 2.688.545;
977°229, 3.397.060, 3.5
No. 22.052, No. 3.527,641, No. 3,61
No. 7,293, No. 3,628,964, No. 3,666
．． No. 480, No. 3,672,898, No. 3,679,
No. 428, No. 3,703,377, No. 3,769,3
No. 01, No. 3,814゜609, No. 3,837,86
No. 2, No. 4,026,707, British Patent No. 1.344
, No. 281, No. 1,507,803, Special Publication No. 43-4
No. 936, No. 53-12,375, JP-A No. 52-11
No. 0.618 and No. 52-109.925.

Along with aggravating pigments, pigments that do not themselves have spectral sensitizing effects or substances that do 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. Although this is most commonly carried out after the completion of chemical sensitization and before application, U.S. Pat.
It is also possible to perform spectral sensitization at the same time as chemical sensitization by adding a chemical sensitizer at the same time as described in JP-A No. 58-113 and No. 4,225,666. 92
It can also be carried out prior to chemical sensitization as described in No. 8. It is also possible to start spectral sensitization by adding it before the completion of silver halide grain precipitation. Furthermore, adding these compounds in portions as taught in U.S. Pat. No. 4,225,666, i.e., adding some of these compounds prior to chemical sensitization and the remainder in It can also be added after sensitization, or at any time during silver halide grain formation, including the method disclosed in U.S. Pat. No. 4,183,756.

The amount added is 4X10-' to 8 per mole of silver halide.
Although it can be used in an amount of X10-3 mol, about 5X10-5 to 2X10-3 mol is more effective when the silver halide grain size is more preferably 0.2 to 1.2 .mu.m.

The various additives mentioned above are used in the photosensitive material related to the present technology, but other various additives can also be used depending on the purpose.

These additives are described in more detail in Research Disclosure Item 17643 (December 1978),
It is described in the same Item 18716 (November 1979) and the same Item 307105 (November 1989), and the relevant parts are summarized in the table below.

(Left below) 2 Sensitivity increasing agent Same as above 3 Spectral sensitizer, pages 23-24 Page 648 right column ~ 99B right ~ Super sensitizer Page 649 right a 998 right 4 Sensitization White
Agent 24 page 998 right 5 Fogging prevention page 1124-25 page 649 right m 99B right ~ and stabilizer 1000
Right 7 Anti-stinting Page 25 Right column 650 left to right column Agent 8 Dye image stabilizer Page 25 9 Hardening agent Page 26 Page 651 Left nil
1004 right to 1005 left 10 Binder 26 pages Same as above 1
003 right to 1004 right 11 Plasticizer, lubricant side Page 27 Page 650 Right column
1006 left - 1006 right 12 Coating aid, pages 26-27 Same as above
1005 Left ~ Surfactant
2006 left 13 static page 27
Same as above 1006 right ~ inhibitor
1007 Left The light-sensitive material of the present invention only needs to have at least one silver halide emulsion layer of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer on the support. There are no particular restrictions on the number or order of the silver emulsion layer and the non-photosensitive layer.A typical example is to deposit a plurality of silver halides with substantially the same color sensitivity but different photosensitivity on the support. This is a silver halide photographic light-sensitive material having at least one light-sensitive layer consisting of an emulsion layer. The photosensitive layer is a unit photosensitive layer that is sensitive to blue light, green light, or red light, and in a multilayer silver halide color photographic light-sensitive material, the arrangement of the unit photosensitive layers is generally as follows: A red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are installed in this order from the support side. However, depending on the purpose, the above-mentioned installation order may be reversed, or the installation order may be such that different photosensitive layers are sandwiched between the same color-sensitive layer.

Non-photosensitive layers such as various intermediate layers may be provided between the above-mentioned silver halide photosensitive layers and between the uppermost layer and the lowermost layer.

The intermediate layer includes JP-A Nos. 61-43748 and 59-1.
No. 13438, No. 59-113440, No. 61-20
Coupler, DIR compound, etc. as described in No. 037 and No. 61-20038 may be included,
It may also contain a commonly used color mixing inhibitor.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are composed of a high-speed emulsion layer and a low-speed emulsion layer, as described in West German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer configuration can be preferably used.

Usually, it is preferable to arrange the halogen emulsion layers so that the intensity of light decreases in sequence toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Also, JP-A-57-
No. 112751, No. 62-200350, No. 62-2
As described in No. 06541, No. 62-206543, etc., a low-sensitivity emulsion layer may be provided on the side far from the support, and a high-sensitivity emulsion layer may be provided on the side close to the support.

To give a specific example, from the side farthest from the support, low sensitivity blue sensitive layer (BL) / high sensitivity blue sensitive layer (BH) / high sensitivity green sensitive layer (GH) / low sensitivity green sensitive layer (GL)/high-sensitivity red-sensitive layer (RH)/low-sensitivity red-sensitive layer (RL), or B H/BL/GL/GH/RH/RL, or BH/BL/G H /G L/RL/RH can be installed in this order.

Further, as described in Japanese Patent Publication No. 55-34932, the blue-sensitive layer/G H/
They can also be arranged in the order of RH/GL/RL. Furthermore, as described in JP-A-56-25738 and JP-A-62-63936, the blue-sensitive layer/GL/RL/GH/RH may be arranged in this order from the farthest side from the support. can.

Furthermore, as described in Japanese Patent Publication No. 4945495, the upper layer is a silver halide emulsion layer with the highest sensitivity, the middle layer is a silver halide emulsion layer with a lower sensitivity, and the lower layer is a silver halide emulsion layer with a higher sensitivity than the middle layer. One example is an arrangement consisting of three layers with different photosensitivity, in which a silver halide emulsion layer with a low sensitivity is arranged, and the photosensitivity decreases sequentially toward the support. Even when it is composed of three layers with different photosensitivity, as described in JP-A No. 59-202464,
In the same color-sensitive layer, medium-sensitivity opalescent layer/high-sensitivity emulsion layer/low-sensitivity emulsion layer may be arranged in this order from the side remote from the support.

In addition, high-sensitivity emulsion layer / low-sensitivity emulsion layer / medium-sensitivity emulsion layer,
Alternatively, they may be arranged in the order of low-speed emulsion layer/medium-speed emulsion layer/high-speed emulsion layer, etc.

Furthermore, even in the case of four or more layers, the arrangement may be changed as described above.

As mentioned above, various layer structures and arrangements can be selected depending on the purpose of each photosensitive material.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide containing about 30 mol% or less of silver iodide. . Particularly preferred is from about 2 mol% to about 10% by mole.
Silver iodobromide or silver iodochlorobromide containing up to mol% silver iodide.

Silver halide grains in photographic emulsions, other than normal crystal grains selenium-sensitized with compounds according to the invention, are cubic, octahedral,
It may have a regular crystal shape such as a tetradecahedron, an irregular crystal shape such as a spherical shape or a plate shape, a crystal defect such as a twin plane, or a composite shape thereof.

The grain size of these silver halides may be fine grains of about 0.2 microns or less, or large grains with a projected area diameter of up to about 10 microns, and they may be polydisperse emulsions or monodisperse emulsions.

Silver halide photographic emulsions other than normal crystals selenium-sensitized with the compound according to the present invention are disclosed, for example, in Research Disclosure+ (RD) NCL17643 (December 1978).
Month).

pp. 22-23, '■, Emulsion production (Emulsion p
118716 (November 1979), p. 648, 307105 (November 1989) + 863-865
Pages and graphics ``Physics and Chemistry of Photography'', published by P. Glafkides, Chemi.
e et Phistque Photography
ue, Paul Motel, 1967), “Photographic Emulsion Chemistry” by Duffin, published by Focal Press (G.
F.

Duffin, Photographic Emul
sion Chemistry (FocalPress
, 1966), “Manufacture and Coating of Photographic Emulsions” by Zelikman et al., published by Focal Press (V.L., Zelik
-man et al, Making and C
oating PhotographicEmujsi
on, Focal Press+ 1964).

U.S. Patent No. 3,574,628, U.S. Patent No. 3,655.39
Monodispersants such as those described in No. 4 and British Patent No. L413,748 are also preferred.

Tabular grains having aspect ratios of about 3 or greater can also be used in the present invention. Tabular grains are described by Gutoff, Photographic Science and Engineering.
ence and Engineering), Vol. 14, pp. 248-257 (1970); U.S. Patent No. 4
, 434,226, 4,414゜310, 4,
433,048, 4,439,520, and British Patent No. 2.112.157.

The crystal structure may be --like, the inside and outside may have different halogen compositions, it may be a layered structure, or silver halides with different compositions may be joined by epitaxial bonding. They may also be bonded with compounds other than silver halide, such as silver rhodan or lead oxide, and mixtures of particles of various crystal forms may be used.

The above-mentioned emulsions may be of the surface latent image type in which the latent image is mainly formed on the surface, the internal latent image type in which the latent image is formed inside the grains, or the type in which latent images are formed both on the surface and inside the grains, but negative type emulsions may be used. It needs to be an emulsion. Among the internal latent image types,
A method for preparing this core/shell type internal latent image type emulsion, which may be a core/shell type internal latent image type emulsion described in JP-A-63-264740, is described in JP-A-59-133542. ing.

The thickness of the shell of this emulsion varies depending on the development process, etc., but is preferably from 3 to 40 nl, particularly preferably from 5 to 20 nl.

The photosensitive material of the present invention includes grain size on the photosensitive silver halide hole side, grain size distribution, halogen composition, grain shape,
Two or more types of emulsions differing in at least one characteristic of sensitivity can be mixed and used in the same layer.

Silver halide grains coated with grain surfaces as described in U.S. Pat. No. 4.082.553, U.S. Pat. No. 4.626,4
No. 98, JP-A No. 59-214852, the silver halide grains and colloidal silver covered inside the grains are applied to a photosensitive silver halide emulsion layer and/or a substantially non-photosensitive hydrophilic colloid layer. It can be used preferably.

Silver halide grains that have their interiors or surfaces covered are defined as - (
refers to silver halide grains that can be developed (non-imagewise). A method for preparing silver halide grains with a fogging inside or on the surface thereof is described in U.S. Pat.

The silver halide that forms the inner core of a core/shell type silver halide grain whose interior is fogged may have the same halogen composition or a different halogen composition. As the silver halide, any of silver chloride, silver chlorobromide, silver iodobromide, and silver chloroiodobromide can be used. Although there is no particular limitation on the grain size of these fogged silver halide grains,
The average particle size is preferably 0.01 to 06758 m, particularly 0.05 to 0.6 μm, and the particle shape is not particularly limited and may be regular particles.
Polydisperse emulsions may be used, but monodisperse emulsions (silver halide grains with a small weight or number of grains (in both cases, 95% of the average grain size is ±4
0% or less) is preferable.

In the present invention, it is preferable to use ultra-photogenic fine grain silver halide. Non-photosensitive fine grain silver halide is a silver halide fine grain that is not exposed to light during imagewise exposure to obtain a dye image and is not substantially developed during the development process, and is preferably not fogged in advance. .

The fine-grain silver halide has a silver bromide content of 0 to 100 mol%, and may contain silver chloride and/or silver iodide as necessary, preferably silver iodide in a content of 0.5 to 100 mol%. It contains 10 mol%.

The fine grain silver halide preferably has an average grain size (average diameter equivalent to a circle of projected area) of 0.01 to 0.5 μm, and preferably 0.01 to 0.5 μm.
02 to 0.2 μm is more preferable.

Fine-grain silver halide can be prepared in the same manner as ordinary photosensitive silver halide. In this case, the surface of the silver halide grains does not need to be optically sensitized, nor is spectral sensitization necessary. However, before adding these to the coating solution, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, or mercapto-based compound or a zinc compound in advance. Colloidal silver can preferably be contained in the silver halide grain-containing layer.

The coating silver amount of the photosensitive material of the present invention is 6.0 g/ls"
The following is preferred, and the most preferred is 4.5 g/+s'' or less.

In addition, in order to prevent deterioration of photographic performance due to formaldehyde gas, US Patent No. 4,411,987 and US Pat.
．． It is preferable to add to the photosensitive material a compound capable of reacting with and fixing formaldehyde as described in No. 435,503.

The photographic emulsion of the present invention is preferably used in color light-sensitive materials, and various color couplers can be used.
A specific example of this is the aforementioned Research Disclosure (R
D) N11I7643, published in the patent described in ■-C-G.

As a yellow coupler, for example, U.S. Patent Nos. 3 and 9
No. 33,501, No. 4,022,620, No. 4
, 326, No. 024, No. 4.401,752, No. 4.248.961, Special Publication No. 58-10739,
British Patent No. 1.425,020, British Patent No. L476.76
No. 0, U.S. Patent No. 3,973.968, U.S. Patent No. 4.31
No. 4,023, No. 4.51L649, European Patent No. 2
49.473A, etc. are preferred.

As magenta couplers, 5-pyrazolone and pyrazoloazole compounds are preferred, and US Pat.
No. 0,619, No. 4,351,897, European Patent No. 73.636, US Patent No. 3,061,432, US Patent No. 3,725.067, Research Disclosure Nt 1.24220 (1984) June), Japanese Patent Application Publication No. 6
No. 0-33552, Research Disclosure 2
4230 (June 1984), JP-A-60-4365
No. 9, No. 61-72238, No. 60-35730, No. 55-118034, No. 60-185951,
U.S. Patent Nos. 4,500,630 and 4.540,6
No. 54, No. 4.565,630, International Publication WO38
Particularly preferred are those described in No. 104795 and the like.

Cyan couplers include phenolic and naphthol couplers, and are described in U.S. Pat. No. 4,052.212.
No. 4,146.396, No. 4,228,23
No. 3, No. 4,296,200, No. 2.369,92
No. 9, No. 2.801,171, No. 2,772.1
No. 62, No. 2,895,826, No. 3.772.
No. 002, No. 3,758,308, No. 4.343
,011, European Patent Publication No. 4,327,173, European Patent Publication No. 3,329,729, European Patent Publication No. 121,36
5 A, No. 249453A, U.S. Patent No. 3,44
No. 6,622, No. 4.333,999, No. 4.7
No. 75.616, No. 4.451,559, No. 4,
No. 427,767, No. 4,690,889, No. 4
．． Preferred are those described in No. 254,212, No. 4,296.199, JP-A-61-42658, and the like.

Colored couplers for correcting unnecessary absorption of coloring dyes are recommended in Research Disclosure 17643.
- Section G, U.S. Patent No. 4,163,670, Japanese Patent Publication No. 1983
-39413, U.S. Patent No. 4,004,929, U.S. Patent No. 4,138.258, U.S. Patent No. 1.146,36
The one described in No. 8 is preferred. Also, U.S. Patent Nos. 4 and 7
No. 74.181, a coupler that corrects unnecessary absorption of a coloring dye by means of a fluorescent dye released during coupling, and a coupler that can react with a developing agent to form a dye, as described in U.S. Pat. No. 4,777,120. It is also preferred to use couplers having a dye precursor group as a leaving group.

Couplers whose coloring dyes have appropriate diffusivity include U.S. Patent No. 4,366.237 and British Patent No. 2.125.
, 570, European Patent No. 96.570, and German Patent Publication No. 3.234,533 are preferred.

Typical polymerized dye-forming couplers include U.S. Pat. Nos. 3,451,820; 4,080,221;
4.367.288, 4.409,320, 4,576.910, British Patent 2.102.1
It is described in No. 73, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. The DIR coupler releasing the development inhibitor is RD17643 as previously described.
, Patents described in sections ■ to F, Japanese Patent Application Laid-Open No. 57-15194
No. 4, No. 57-154234, No. 60-184248
Preferred are those described in U.S. Pat. No. 63-37346, U.S. Pat.

A coupler that can be particularly preferably used in the present invention is
No. 1-201247 or Research Disclosure N
(111449 (October 1973)). It is preferably used in red angry silver halide emulsion layers, especially close to the support, and is usually a phenolic type, preferably a naphthol type coupler. It is a coupler that can release, for example, β-mercaptopropionic acid from the leaving group of the residue.It can eliminate the defective desilvering that occurs when the light-sensitive material of the present invention containing a tabular emulsion is rapidly developed.

Other couplers that can be used in the photosensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4,130,427, etc., U.S. Pat. , DIR redox compound releasing couplers, DIR coupler releasing couplers described in JP-A-60-185950, JP-A-62-24525, etc.,
DIR coupler releasing redox compound or DIR redox releasing redox compound, European Patent No. 173.3
02A, R, D, N [11144
9, No. 24241, bleach accelerator releasing coupler described in JP-A-61-201247, etc., U.S. Pat. No. 4,553
, No. 477, etc., Gantt release coupler, JP-A-6
Examples thereof include a coupler that releases a leuco dye described in US Pat. No. 3-75747 and a coupler that releases a fluorescent dye described in US Pat. No. 4,774,181.

The color photosensitive material of the present invention includes JP-A-63-2577
No. 47, No. 62-272248, and JP-A-1-8
1,2-benzisothiapurine-3 described in No. 0941
-one, n-butyl-p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol,
It is preferable to add various preservatives or antifungal agents such as 2-phenoxyethanol and 2-(4-thiazolyl)benzimidazole.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, annex 17643, page 28, and annex 18716, 6
It is described from the right column on page 47 to the left column on page 648.

In the photographic material using the photographic emulsion of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less,
More preferably, it is 20 μI or less. Also, membrane swelling rate TI/□
is preferably 30 seconds or less, more preferably 20 seconds or less.

The film thickness means the film thickness measured at 25° C. and under 55% humidity control (2 days), and the film swelling rate T I/□ can be measured according to a method known in the art.

For example, Photographic Science and Engineering (Photogr, Sci, Eng,) by Green et al.
It can be measured by using a swelling meter (swelling membrane) of the type described in Vol. 19, No. 2, pp. 124-129. TI/□ is defined as the time required to reach 1/2 of the saturated film thickness, with 90% of the maximum swollen film thickness reached when treated with a color developer for 13 minutes and 15 seconds at 30° C. as the saturated film thickness.

The membrane swelling rate TI/□ is determined by adding hardener 1 to gelatin as a binder.1. Alternatively, it can be adjusted by changing the aging conditions after application. Further, the swelling rate is preferably 150 to 400%.

The swelling ratio is calculated from the maximum swollen film thickness under the conditions described above according to the formula: (maximum swollen film thickness - film thickness)/film thickness.

The color photographic material according to the present invention includes the above-mentioned RD, N
α17643 pages 28-29, and Nα18716
615, left column to right column.

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

Silver halide color photographic light-sensitive materials using the photographic emulsion of the present invention are generally subjected to water washing and/or stabilization steps after desilvering treatment. The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), 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. It can be set in a wide range depending on the situation.

Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is described in the Journal of the 5ociet.
y of Motion Picture and Te
1evision Engineers Volume 64, P.
248-253 (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 bacteria may multiply due to the increased residence time of water in the tank, and the resulting floating substances may adhere to the photosensitive material. A problem arises. In the processing of the color photosensitive material of the present invention, as a solution to such problems,
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
Chlorinated disinfectants such as isothiazolone compounds, cyabendazole, chlorinated sodium isocyanurate, etc., pendotriazole, etc., described in the issue, by Hiroshi Horiguchi [Chemistry of antibacterial and fungicidal agents J (1986), Sankyo Publishing, Hygiene "Microbial sterilization, sterilization, and anti-mildew technology J (1982)" edited by the Society of Industrial Engineers and the Japanese Society of Anti-bacterial and Anti-Mold Agents (1)
It is also possible to use the fungicides described in 1986).

The pH of the washing water in the processing of the photosensitive material of the present invention is 4 to 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 to 45°C, preferably 30 seconds to 5 minutes at 25 to 40°C. A range of minutes is selected. Furthermore, the photosensitive material of the present invention may be washed with water instead of washing with water.
Can be treated directly with stabilizing solution. In such stabilization treatment, Japanese Patent Application Laid-Open Nos. 57-8543 and 5B
All known methods described in Japanese Patent No. 14834 and No. 60-220345 can be used.

Furthermore, subsequent to the water washing treatment, a further stabilization treatment may be performed. An example of this is a formalin bath used as a final bath for color photosensitive materials for photography.

[Examples] Example 1 (Preparation of octahedral emulsion) Into an aqueous solution in which potassium bromide and gelatin were added and dissolved in a reaction vessel and maintained at 75°C, silver nitrate f4 solution and potassium iodide were added with stirring. and potassium bromide 3:9
The aqueous solution mixed and dissolved at a ratio of pAg7.7.
It was added by the so-called controlled double jet method while maintaining the temperature at 9.9.

After the addition, the temperature was lowered to 35°C, soluble salts were removed by the usual flocculation method, and then the temperature was lowered to 40°C again.
The temperature rose to . Next, add 60g of gelatin per mole of silver.
Additional addition ε1 was added and the pH was further adjusted to 6.8.

The thus obtained grains were octahedral with an equivalent sphere diameter of 0.7 μm and contained 3 mol % of silver iodide. Moreover, pAg at 40°C was 8.4.

(Preparation of cubic emulsion) Potassium bromide and gelatin were added and dissolved in an aqueous solution kept at 75°C in a reaction vessel, and an aqueous silver nitrate solution, potassium iodide and potassium bromide were added in a ratio of 3:9 with stirring.
pAg6.7 and the dissolved aqueous solution at a ratio of 7
It was added by the so-called controlled double jet method while maintaining the temperature.

After the addition was completed, the temperature was lowered to 35°C, soluble salts were removed by the usual flocculation method, and then the temperature was raised to 40°C again. Next, 60 g of gelatin was added per mole of silver ε1, and the pH was adjusted to 6.8, and the pAg was adjusted to 4.
Adjusted to 8.4 at 0°C.

The particles thus obtained were cubic with an equivalent sphere diameter of 0.7 μm and contained 3 mol % of silver iodide.

(Preparation of twin emulsion) Into an aqueous solution in which potassium bromide, thioether and gelatin were added and dissolved and kept at 75°C, silver nitrate solution, potassium iodide and potassium bromide were mixed in a ratio of 3:97 while stirring.
and an aqueous solution mixed and dissolved at a ratio of 1.0 to 2.0 and added by a double jet method while maintaining the pAg at 9.1.

After the addition was completed, the temperature was lowered to 35°C, soluble salts were removed by the usual flocculation method, and then the temperature was lowered to 40°C again.
The temperature was raised to C. Next, add 60g of gelatin per mole of silver.
Further, the pH was adjusted to 6.8 by adding ε1.

The thus obtained grains were twin crystals with an equivalent sphere diameter of 0.7 μm and contained 3 mol % of silver iodide.

The resulting emulsions were each chemically sensitized. At 56°C, the pigment anhydro-5-chloro-5'-phenyl-9-
Ethyl-3,3'-di(3-sulfopropyl)oxacarbocyanine hydroxide sodium salt was added to form octahedrons at 370 μ/AgX mol, cubes at 380 μ/Ag, and twins at 390 μ/AgX mol. In addition, the sensitizers shown in Table 1 were also added.

Further, 9 Xl0-' mol/Agχ of chloroauric acid and 2.5 X 10-' mol/Agχ of potassium thiocyanate were added, followed by chemical ripening for 30 minutes.

After completion of chemical sensitization, the following compounds were added and coated together with a protective layer on a triacetyl cellulose film support having an undercoat layer by coextrusion method.

(1) Emulsion layer O emulsion... Emulsion shown in Table 1 ○ Coupler, tricresyl phosphate, stabilizer 4-hydroxy-6-methyl-13,3a
, 7-tetrazaindene, Coating aid Sodium dodecylbenzenesulfonate (2) Protective layer, Polymethyl methacrylate fine particles, 2,4-dichloro-6-hydroxy-5-triazine sodium salt, Gelatin These samples were subjected to sensitometry. exposure (1/100 second) was applied, and the following color development process was performed.

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, established ・・・ 6 minutes 3
0 seconds 5, wash with water 3 minutes 15 seconds 6, low
3 minutes and 15 seconds The processing composition used in each step is as follows.

Sodium nitrilotriacetate 1.0 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-
β-hydroxyethylamino)-2-methyl-aniline sulfate 4.5 g Add water 111a Ammonium bromide 160.0 g Aqueous ammonia (28%) 25.0 d Ethylenediamine-tetraacetic acid sodium salt 130 g Glacial acetic acid
Add 14d water
11 feet 11 Sodium tetrapolyphosphate 2.0g Sodium sulfite 4.0g Ammonium thiosulfate (70%) 175.0d Sodium bisulfite 4.6g Add water
11 Subcondyle formalin 8. After adding Od water, the concentration of the 12 treatment agent samples was measured using a green filter.

Sensitivity is defined as the amount of exposure that gives a density of fog + 0.1,
It is expressed as a relative value with the value of sample 1 as 100. Table 1 shows the strength and sensitivity values.

In addition, evaluation of graininess was performed as follows. Samples 1-2
No. 8 was exposed to light giving a density of fog +0.5, and developed under the above-mentioned processing conditions. The density of the sample was measured using a microdensitometer with a green filter to determine the RMS granularity. The results are expressed as relative values with the RMS granularity of Sample 1 as 100, and these values are shown in Table 1.

From the results in Table 1, it can be seen that when a twin emulsion is used, the emulsion selenium-sensitized by the compound of the present invention is accompanied by deterioration of graininess, but when a normal crystal emulsion is used, there is no deterioration of graininess. It can be seen that sensitivity amplifier can be achieved.

Example 2 In the following, normal crystal grains having parts with different halogen compositions inside have high sensitivity, but the concentration decreases significantly due to pressure, whereas halogen inside the selenium sensitized by the compound of the present invention Normal crystal grains having different compositions have higher sensitivity and are also more effective in preventing concentration reduction due to pressure.

(Twinned emulsion with parts with different halogen compositions) 65°
Silver nitrate and silver iodide aqueous solutions were added to a gelatin solution maintained at a pH of
Silver iodide with a grain size of 0.18 μm was prepared by adding the silver iodide while maintaining the gl2.

This silver iodide emulsion was added to an aqueous gelatin solution, pAgs,
Adjusted to 6. Subsequently, an aqueous solution of silver nitrate and ammonium bromide was added by a so-called controlled double jet method while maintaining pAgs, s. The temperature was maintained at 75°C during the addition. Up to this point, silver iodobromide containing an average of 24 moles of silver iodide has been formed. followed by pAgs,
After adjusting the pAgs to 4, silver nitrate and potassium bromide aqueous solutions were added using a controlled double jet method while maintaining the pAgs at 4.

After going through the normal desalting process, gelatin is added to
The pH was adjusted to 6.8 and the pAgs to 4 at 140°C. This was designated as emulsion A. The average particle size is 0.
It was a silver iodobromide emulsion with a grain size of 99μ and an average of 12 moles of silver iodide.

(Normal crystal emulsion with different internal halogen compositions) After adding ammonia equivalent to 1% by volume to a gelatin solution containing potassium bromide kept at 65°C, add silver nitrate aqueous solution and iodide while stirring. An aqueous solution containing potassium and potassium bromide mixed at a ratio of 3:97 and pAg
It was added by the so-called controlled double jet method while maintaining the temperature at 7.9. Additions continued until the amount of silver nitrate used was 5% of the total amount used.

Subsequently, while stirring, an aqueous silver nitrate solution and an aqueous solution in which potassium iodide and potassium bromide were mixed and dissolved in a ratio of 24 to 6 were added by a controlled double jet method while maintaining pAgl at 7.

Additions continued until the amount of silver nitrate used was 49% of the total amount used.

Subsequently, a silver nitrate aqueous solution and a potassium bromide aqueous solution were added by a controlled double jet method while maintaining the pAgs at 2 while stirring. Additions continued until the amount of silver nitrate used was 46% of the total amount used.

6 gelatin per mole of silver after the normal desalting process.
The pH was adjusted to 6.8 and the pAgs to 4 at 140°C. The obtained emulsion was designated as Emulsion B.

Emulsion B has an average grain size of 0.90μ, and a silver iodobromide layer containing 5 mol of silver iodide, which accounts for 5% in order from the center, and a silver iodobromide layer containing 49
a silver iodobromide layer containing 24 moles of silver iodide accounting for 46% of silver iodide;
They are normal crystal octahedral grains with a triple structure composed of a pure silver bromide layer that accounts for % of the silver bromide layer.

A silver iodobromide layer containing 5 moles of silver iodide accounting for 25%, a silver iodobromide layer containing 37 moles of silver iodide accounting for 29%, and 46 Normal-crystal octahedral grains with a triple structure composed of pure silver bromide layers accounting for % of the silver bromide layer were prepared.

This was designated as Emulsion C. The average particle size was 0.9μ.

After dividing the obtained emulsions A to C into three parts each, 56
Sensitizing dye I, sensitizing dye ■ shown in Table B at the end in °C,
After adding the sensitizing dye ■ in the amount shown in the photosensitive layer composition below,
9.2 x 10-' mol 1 mol Ag of chloroauric acid, 3.0 x 10-' mol 1 mol Ag of potassium thiocyanate, and further added sodium thiosulfate and selenium sensitizer in the amounts shown in Table 3. Optimally chemically sensitized.Here, "optimally chemically sensitized" means 1/100 after chemical sensitization.
Chemical sensitization that achieves the highest sensitivity when exposed for seconds.

on a subbed cellulose triacetate film support.
Samples 29 to 37, which are multilayer color light-sensitive materials, were prepared by applying layers having the compositions shown below.

(Photosensitive layer composition) The numbers corresponding to each component indicate the coating amount expressed in g/rd units, and for silver halide, the coating amount is expressed in terms of silver. However, regarding the sensitizing dye, the coating amount per mole of silver halide in the same layer is shown in mole units, and the components listed in Table C at the end are used below. Emulsion D- is also listed in the table below.

[Sample 29] First layer (antihalation layer) Black colloidal silver Silver 0.18 Gelatin 1.40 Second layer (intermediate layer) 2.5-di-t-pentadecylhydroquinone 0.18EX-1
0,070 E X -30,020 E Layer (first red-sensitive emulsion layer) Emulsion D Silver 0.25 Emulsion E
Silver 0.25 Sensitizing dye 1
6.9 Xl0-' Sensitizing Dye I
I 1.8 Xl0-' Sensitizing dye 1 [3, I Xl0-' E Gelatin 0.87 4th layer (second red-sensitive emulsion layer) Emulsion I Silver 1.00 Sensitizing dye 1 5.1 Xl0-' Sensitizing dye II 1.4 Xl0-'
Sensitizing dye III 2.3X10
-'E X -20,40 E X -30,050 E Chemically sensitized emulsion prepared in this example Silver 1.60E
-20,097 E X -30,010 E X -40,080 HB S -10,22 HB S -20,10 Gelatin 1.63 6th layer (middle layer) E 020 Gelatin 0.80 7th layer (first green-sensitive emulsion layer) Emulsion D ffl
0.15 emulsion E if!
0.15 sensitizing dye IV 3
．． 0X10-'sensitizing dye V 1
．． OXl0-'sensitizing dye VI
3.8 Xl0-'EX-10,021 E 2. Green-sensitive emulsion layer) Emulsion F Silver 0.45 Sensitizing dye IV 2. I Xl0-'
Exacerbating pigment V7. OXl0-
'Sensitizing dye Vl 2.6X10
-'E X -60,094 E X -70,026 E 1.20 Sensitizing Dye IV 3.5 Xl0-' Sensitizing Dye V B, 0X10-' Sensitizing Dye Vl 3. OXl0-
'E X -10,02S E X -110,10 E
Layer (yellow filter layer) Yellow colloidal silver Silver 0.050E
X -50,080 HB S -10,030 Gelatin 0.95 No. 11
Layer (first blue-sensitive emulsion layer) Emulsion D w & 0.080 Emulsion E Silver 0.070 Emulsion H Silver 0.070 Sensitizing dye ■ 3.5 X 10-
'EX -80,042 EX -90,72 HB S -10,28 Gelatin 1.10 No. 12
Layer (second blue-sensitive emulsion layer) Emulsion I iIO, 45 sensitizing dye ■ 2. I Xl0-'EX
-90,1S EX -107,0xlO-" HB S -10,050 Gelatin 0.78 No. 13
Layer (third blue emulsion layer) Emulsion J! J! 0.
77 sensitizing dye ■ 2.2 Xl0
-'E
-40,11 0-50,17 HBS-15,0X10-” Gelatin 1.oO No. 15
Layer (second protective layer) H-10,40 B-1 (diameter 1.7 μm) 5.0xlO-
"B-2 (diameter 1.7μm) 0.10
B-30,1O 3-10,20 Gelatin 1.20 Furthermore, in order to improve storage stability, processability, pressure resistance, anti-mildew/bacterial properties, antistatic properties and coating properties, W-1 is added to the entire layer. , W-2, W
-3, B-4, B-5, F-1, F-2, F-3, F-
4, F-5, F-6, F-7, F-8, F-9, F-1
0, F-11, F-12, F-13 and iron salt, lead salt,
Contains gold salt, platinum salt, iridium salt, and rhodium salt.

In Sample 29, the third red-sensitive emulsion layer uses Emulsion A that has been optimally chemically sensitized using the compounds shown in Table 3.

In samples 23 to 37, the emulsions used in the third red-sensitive emulsion layer were emulsions A to C which were optimally chemically sensitized using the compounds in Table 3.

After image exposure, the same development process as in Example I was performed.

Regarding the characteristic curve of the cyan color image, Table 3 shows the fog defined by the fog fil and the relative value of the reciprocal of the exposure amount that gives a density 0.1 higher than the fog density.

Graininess was evaluated as follows.

The same development process as in Example 1 was performed on a sample that had been exposed to give a density of cyan image fog +0.5.

Thereafter, the density was measured using a microdensitometer with a red filter to determine the RMS granularity. Sample 29 results
It is expressed as a relative value with the RMS granularity of 100 as shown in Table 3.

The decrease in concentration due to pressurization was evaluated as follows.

Samples 29 to 37 are wrapped around a cylinder with a diameter of 5 - at an angle of O.

to 180' for 10 seconds at a speed similar to -. Thereafter, the sample was returned to its original position and exposed to light such that the density of the non-bent portions was 1.0, and then the same development process as in Example 1 was performed. The density of the cyan image was measured, and the reduction in the density of the bent part relative to the density of the other parts was defined as the density reduction due to pressurization, and this value is shown in Table 3.

The following can be seen from the results in Table 3. First, in comparing products that have internal parts with different halogen compositions,
In twin emulsions, selenium sensitization with the compound of the present invention is accompanied by deterioration of graininess. However, when normal crystals are used and selenium sensitized with the compound of the present invention as in the present invention, sensitivity is increased without deterioration of graininess.

Second, in normal gold-sulfur enrichment, normal crystals, which have internal parts with different halogen compositions, have a larger concentration drop in the pressurized part than twin emulsions, which have internal parts with different halogen compositions. However, this drawback can be overcome if selenium sensitization is performed using the compound of the present invention.

(Example 3) By applying the normal crystal particle formation method shown in Example 2, the average particle size was 0.9 μm, the entire particle had a uniform composition,
Silver iodobromide octahedral emulsions containing 3 mol and 6 mol of silver iodide were prepared and designated as emulsions E. This emulsion, E, and emulsions B and C prepared in Example 2 were chemically sensitized. Maintaining the temperature at 56°C, 4-hydroxy-6-methyl-1
,3,3a,7-tetrazaindene at 500■/AgX
After addition of 9x10-' mol/AgX mol of chloroauric acid, 2x10-' mol/AgX mol of potassium thiocyanate, and further addition of sodium thiosulfate in the amount shown in Table 4, or the amount shown in Table 4. After adding the selenium enhancer, it was aged for 30 minutes.

After that, samples 38 to 53 were coated in the same manner as in Example 1.
was created.

Exposure and development were performed in the same manner as in Example 1, and fog, sensitivity, and graininess were evaluated. All evaluations were conducted in the same manner as in Example 1, and the values of sample 38 were 1 for sensitivity and graininess.
It is expressed as a relative value with 00. The results are shown in Table 4.

As is clear from the results in Table 4, the effect of selenium sensitization by the compound of the present invention is manifested regardless of the presence or absence of parts with different halogen compositions inside. However, it can be seen that normal crystals that have internal portions with different halogen compositions have significantly higher sensitivity or superior graininess than normal crystals that do not.

(Effects of the invention) By using normal crystals selenium-sensitized with the compound of the present invention, it is possible to achieve high sensitivity that was previously unobtainable with low fog, and also prevents scratch sensitization and pressure desensitization. A photosensitive material was obtained.

(Margin below) Table A CH31 e I-4Sp Hs CH.

ζp ■-10 CH3 ■ L Hs ■-13 Se Se " C.B.

■-15 Se 〇H1 ■-16 s Cl.

■-17 ■-19 ■-20 H3 ■-22 ■-23 ■-24 I CII CII ■-25 ■-27 ■-28 CHx L;t13 L;t13Se 1[1-2 Se 1[[-3 Se (a I[[-5 3ρ I[1-6 Se Se I-8 Se 1[[-9 qρ ■-10 (a ■-11 Se ■-12 ■-13 ts ■-14 <Q (a 1[ 1-16 (a ■-17 m-18 1 [[-19 ■-20 ■-22 ■-23 e ■-24 ■-25 ■-26 '=p ■-27 e ■-28 e ■-29 e ■-30 ■-32 ■-33 ■-34 e ■-35 e ■-36 t- ■-37 O ■-38 e ■-39 e ■-40 e ■-41 ■-43 (a ■-44 ■ -45 e ■-46 e ■-47 e ■-J Table B Exacerbating dye I Exacerbating dye ■ Sensitizing dye ■ Table C X-3 X-4 II X-6 mol, @t, l!;'J'lυ , UUUX-7 EX-10 nL+ H3 EX-11 EX-12 CtHs CJsC!11.Os
Oρ EX-13 1;l N(C寞H3J3 Sensitizing dye ■ Sensitizing dye ■ Sensitizing dye V Sensitizing dye ■ Sensitizing dye ■ ' C0OHC00CHz COOHC00CHz CM, ct+s (CH3) 5siO→5i-0+ry÷5i-0±■
-5i(CHs)s→CHz-C8-+-+CHz-C
FI±-, -x/y=70/30H Procedural amendment Heisei also, i, il day

Claims (4)

[Claims] (1) A silver halide characterized by having at least one silver halide emulsion layer containing normal crystal silver halide grains sensitized with selenium with at least one compound represented by the following general formula (I). Photographic material. General formula (I) ▲There are numerical formulas, chemical formulas, tables, etc.▼ In the formula, R_1, R_2, R_3, R_4 are alkyl groups, cycloalkyl groups, alkenyl groups, alkynyl groups, aralkyl groups, aryl groups, heterocyclic groups, acyl groups , represents a carboxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, and a sulfamoyl group. However, R_1 to R_4 are not all methyl groups. (2) The silver halide photographic material according to claim (1), wherein the general formula (I) is represented by the following general formula (II). General formula (II) ▲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. (3) A silver halide photographic material having at least one silver halide emulsion layer containing normal crystal grains sensitized with selenium with at least one compound represented by the following general formula (III). General formula (III) ▲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,
It represents 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, and a sulfamoyl group. However, R_8 and R
_9, R_9 and R_1_0, R_1_0 and R_1_1,
At least one pair of R_1_1 and R_8 shall be combined with each other to form a ring. (4) The photographic light-sensitive material according to any one of claims (1) to (3), wherein the normal crystal grains have internal portions with different halogen compositions.