JPH01284848A - Negative type silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the sensitivity of the title material, and to lessen the inherent desensitization due to a color matter by specifying the silver iodide content of a silver halide particle contd. in the emulsion of an emulsion layer, and composing the silver halide particle of a specified twin crystal particle. CONSTITUTION:The photographic sensitive material comprises at least one layer of the silver halide emulsion layer provided on a supporting body. In the photographic sensitive material, the silver halide particle which is contained in the emulsion contd. in at least one layer of the emulsion layers and is chemically sensitized, is composed of the outer-most layer (shell part) (1) of the particle having the silver iodide content of >=6mol.% and the inner phase (core part) (2) which has a lower silver iodide content than that of the outer-most layer by >=3mol.%. And, the phases (1) and (2) are composed of the twin crystal particle which is clearly divided into the shell part and the core part and has an aspect ratio of <=8. As mentioned above, as the silver halide particle has a higher silver halide content in the shell part than that of the core part and has a layer structure capable of clearly dividing into the shell part and the core part, the inherent desensitization of the silver halide particle due to the color matter does not generate.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide photographic material.

(Prior Art) The basic properties that have been and are still required for photographic silver halide include high sensitivity, low fog density, excellent graininess, and high development activity. Furthermore, it has excellent color sensitization properties.

Used as silver halide in photographic emulsions. These include silver iodide, silver bromide, silver chloride, and their composite 7c microcrystalline particles. Generally, these fine particles absorb only a portion of visible light. Therefore, it is not possible to obtain a complete color photographic emulsion by using only the light absorption inherent in silver halide. Therefore, when used in color photographic emulsions (currently even when used in black and white photographic emulsions), dyes are adsorbed to perform so-called color sensitization. When performing color sensitization,
Silver chloride (silver bromide, silver iodide, in that order) has stronger dye adsorption.

Most of the halogenated fine particles for negatives that are currently made into powdered products are O-several ma to ensure sufficient adsorption for color sensitization.
The surface contains 1% silver iodide.

However, on the other hand, there is a problem in that the photoresponse sensitivity of silver halide fine grains becomes significantly desensitized (dye desensitization) when a dye is adsorbed. In order to obtain an excellent color sensitized emulsion, a technique that does not cause dye desensitization is essential and highly desired.

As will be detailed later, improvement in dye desensitization has been achieved by the present invention, but one of the fundamental deficiencies of this technique is that the surface silver iodide content is as high as 6 moL or more. It is conventionally known that particles with a high iodine content on the surface are undesirable as negative photographic materials because the progress of development is significantly delayed.

For example, J, Photo, 8ci, 2≠
, Riza (/976) has an iodine content of 1g in the shell part.
and 36 mon% core/shell type particles. Tokukai Sho A again! -/9g da 3 has core/
There is a description of a color reversal photographic Mc source material that is shell type and in which the silver iodide content of the shell is higher than the silver iodide content of the core. It is intended to reduce the sensitivity increase rate and contrast of photosensitive development, and is unsuitable for use in negatives. In addition, JP-A-Sho≠Ta-90 Octopus θ and Do-Ko Tata 072/No. have grains in which the core is military and the shell is made of silver iodobromide, and the silver iodide content of the shell is J, /θ, or /j man% example is low, but it is used directly in a positive emulsion and is inappropriately used in a negative emulsion. Tokukai Akira! l
, -7j #3/ has a surface silver iodide content of 6 to gmo.
An example of a monodisperse grain having a surface silver iodide content of 1% is disclosed, but the grain has a surface silver iodide content of 3 m2 in the same emulsion layer.
oj! It is said that it is effective only when used with particles of less than %, and that the former alone has low sensitivity.

For Mayoji Kaisho 60-/#7727, the difference in average silver iodide content between two adjacent layers is more than / Q moa, and the silver iodide content in the outermost layer is less than 4tOmoi,%. A certain multilayer structure particle is described in the claims, and the preferred iodized steel content ratio of the outermost layer is described as O to 10 moi.%. Furthermore, the silver iodide content of the outermost layer of the grains described in the Examples is all 3 m02 or less.

An example of grains with a high silver iodide content in the outermost layer is JP-A-3G-
//39', No. 27, the grains were tabular grains with an average aspect ratio larger than g:l.

As used herein, the ast ratio is the ratio of the equivalent circle diameter of the projected area (hereinafter referred to as D circle) to the grain thickness. Particles with a high aspect ratio deteriorate graininess and are not preferred as photographic materials. and the tabular grain has two parallel major faces that can be rotated and a central region extending between the two major faces,
The iodide content in the central region is also lower and more iodide than in the at least one laterally disposed region extending between the two major planes.

Example of particles with a clear double structure/RI JP-A-60-7
μ33/, the grains in this patent are specified that the outermost layer is silver halide microcrystals containing silver iodide of Jmo β or less. As mentioned above, conventional technology for using grains with a surface silver iodide content of 6 mon% or more in a practical negative emulsion has not been established.

Regarding the second-order heavy structure particles, for example, JP-A-6/-Jμ
No. 313/ and No. 62-/3/2≠7, both of which have lower silver iodide content in the outermost layer than in the inner part of the outermost layer. Even in the 7'C example, the silver iodide content in the outermost layer was l, mol! There are no cases where it is more than %.

(Objective of the Invention) An object of the present invention is to provide a negative silver halide photographic W& source material which is highly sensitive, has little inherent desensitization due to dyes, and has excellent graininess.

(Structure of the Invention) An object of the present invention is to provide a photographic W&light material having at least seven silver halide emulsion layers on a support, in which a chemically sensitized silver halide emulsion contained in one of the emulsion layers is provided. The silver halide grains have a silver iodide content of the outermost layer (shell part) of lsmofl.
It's more than Chi■ It's narrowest inside than that! The silver iodide content is higher than 3
A silver halide negative photographic light-sensitive material characterized by having a phase (core part) with less than 1% of mal and being twinned grains with an aspect ratio of g or less that allows the phases of ■ and ■ to be clearly distinguished. achieved.

The main reason why the grains of the present invention do not cause inherent desensitization due to dyes is that the silver iodide content of the outermost layer of Vi is high, and that the outermost layer (core part) and the shell part have an f-shaped structure that can be clearly distinguished. It is something that we have.

The clear layered structure mentioned here can be determined by the method of X+W diffraction. An example of applying X-ray diffraction to silver halide grains can be found in H. Hirsch's Journal of Photographic Science Vol. 10 (/96.2).
, pages 29' onwards. When the lattice constant is determined by the halogen @ formation, Black's condition (jdsin
A diffraction peak occurs at a diffraction angle that satisfies θ=nλ)1.

Regarding the measurement method of X-ray diffraction, please refer to Basic Analytical Chemistry Course 2ti.
It is described in detail in "X-ray analysis" (Kyoritsu Shuppan) and "X-ray diffraction guide" (Rigaku Denki Co., Ltd.). The standard measurement method is to use Cu as a target and obtain the diffraction curve of the (,12Q) plane of silver halide using β rays as a radiation source (tube voltage ≠ OKV, tube flow Omk). . In order to improve the resolution of the foot measuring device, we measured the width of the slit (divergent slit, light receiving slit, etc.), the time constant of the device, the scanning speed of the goniometer, and the recording speed using a standard sample such as silicon. It is necessary to check the accuracy of the feet.

When emulsion grains have two distinct layered structures, a diffraction maximum due to halocarbon activation in the high iodine layer and a diffraction maximum due to silver halide in the low iodine layer form a single peak in the diffraction curve.

In the present invention, the substantially d distinct layered structure is defined by the (120) plane of silver halide using β rays for Cu with a diffraction angle (,7!θ) in the range of 31''' to μd0. When a curve of diffraction intensity versus diffraction angle is obtained, there is a diffraction peak corresponding to a high iodine layer containing 10 to 1A3 moles of iodide, and a diffraction peak corresponding to a low iodine layer containing less than j moles of silver iodide. There are two diffraction maxima and seven minima between them,
and the peak diffraction intensity of the layer with a high silver iodide content is equal to or less than the peak diffraction intensity of the layer with a low silver iodide content.
// indicates the case. Preferably / is the case where it becomes ~//l.

The method of completely decomposing a diffraction curve made up of two diffraction components is well known, for example, in the Experimental Physics Course//
It is explained in books such as Lattice Defects (Kyoritsu Shuppan).

It is also useful to assume that the curve is a function such as a Gauss function or a Lorentz function and to analyze it using a curve analyzer manufactured by Du Pont.

Even in the case of an emulsion in which two grains having different halogen compositions coexisting without having a clear layered structure, two peaks appear in the X-ray diffraction.

As described above, emulsions cannot exhibit the excellent photographic performance obtained by the present invention.

In order to determine whether a silver halide emulsion is an emulsion according to the present invention or an emulsion in which two types of silver halide grains coexist as described above, in addition to the X-ray diffraction method, EPMAi (
Electron-Probehaicro Anal
This is possible by using yzer[)g.

In this method, a well-dispersed sample is prepared so that the emulsion grains do not come into contact with each other, and then an electron beam is irradiated. Elemental analysis of extremely small parts can be performed by X-ray analysis using electron beam excitation.

By this method, 4! By determining the characteristic X6 intensity of iodine and iodine emitted from r'E1 particles, the halogen composition of each particle can be determined.

If the halogen composition of at least 50 grains is completely confirmed by the EPMA method, it can be determined whether the emulsion is an emulsion according to the present invention or not.

In the emulsion of the present invention, it is preferable that the iodine content among grains is more uniform.

It is preferable that the relative standard deviation of the distribution of iodine content between particles is measured by the EPMA method and is less than JO, more preferably less than 3J%, particularly less than JO'4.

Preferred halogen compositions of the silver halide grains having a clear layered structure of the present invention are as follows. (See Table A) Table A Examples of iodine content (m02%) of each layer in a preferred layered structure Consists of chemical silver. The shell part has a silver iodide content of 6 m02 or more and 3 m0 less than the core part.
Consists of 2% or more silver iodobromide or silver chloroiodobromide. Preferred silver iodide content to reduce dye desensitization is 1 mo
% or more, particularly preferably /λmo1. It is more than 1. In addition, from the viewpoint of development progress, the average silver iodide content of the entire grain is preferably 10 m0β or less, and particularly preferably j
; mop, % or less. The ratio of the amount of silver in the core to the amount of silver in the shell (core/shell ratio) is preferably 1.
or more, and particularly preferably λ or more and j or less.

Although there is no particular limitation on the size of the silver halide grains having a clear layered structure according to the present invention, it is preferable that the equivalent sphere diameter is 0.2 μm or more. Further, the grain type may be a tabular twin crystal, or a twin crystal having an irregular crystal shape such as a spherical shape or a potato shape.

The silver halide grains of the present invention preferably account for 30% or more (projected area) of all silver halide grains in the emulsion,
In particular, it is preferably 70 inches or more, and more preferably 70% or more.

Although the emulsions of the present invention can have a wide grain size distribution, emulsions with a narrow grain size distribution are preferred. Particularly preferred is a monodispersed emulsion in which the size of the grains occupying 70 inches of the total of each emulsion is within ±qO% of the average grain size, and more preferably within ±3030 inches with respect to the weight of silver halide grains or the number of grains.

The emulsion of the present invention having a distinct layered structure is known in the field of silver halide photographic materials, and fc'! It can be prepared by selecting and combining the following methods.

First, to prepare the core particles, methods such as the acidic method, neutral method, and ammonia method can be selected, and methods for reacting soluble silver salt and soluble halogen salt can be selected from one-sided mixing method, simultaneous mixing method, and combinations thereof. .

As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a controlled double jet method can also be used. Another type of simultaneous mixing method is the triple jet method, in which soluble halogen salts of different compositions are mixed independently (e.g., soluble silver salt and soluble method).

elementary terms) can also be used. As a method for supplying halogen and silver when the core grain is a mixed crystal, it is preferable to add silver halide fine grains having the same halogen composition as the core grain to be formed. In this case, the size of the iron fine particles is preferably 0.1 μm or less, particularly 0.03 μm.
The following are preferred.

Maku Tokko Akira μ! It is also possible to use the method of accelerating the addition rate over time as disclosed in U.S. Pat. One of these methods is effective for improving the monodispersity of particles.

Core particles are prepared using ammonia, rhodan salt, thioureas,
It is possible to carry out the process in the presence of a silver halide solvent such as a thioether or an amine, or it is also possible to carry out the process without a solvent.

It is desirable that the core particles have high monodispersity, and therefore the pBr at the time of nucleation is preferably 1.30 or more.

The temperature at the time of nucleation is set to AO to increase the probability of twin generation.
' C or less is preferable, and ≠Q C or less is particularly preferable. When growing prophase nuclei, pBr/ is preferably 70 or more, especially 2. 3 from QO
．． OO is preferred. The temperature during particle growth may be any temperature that can dissolve the dispersion medium, but preferably from 110°C to ♂
It is 0°C.

When forming core particles, electron traps such as silver nuclei should not be introduced into the core particles, and therefore the pH is preferably 7.0 or less, and particularly preferably 6.0 or less.

Various gelatins or synthetic polymers can be used as the dispersion medium when forming the Mayu core particles. Examples of synthetic polymers include polyvinyl alcohol, polyvinyl bialidone, polyacrylamide, dextran, and the like.

The core grain has a silver iodide content of 3 to speed up the development progress.
m02% or less is preferable, particularly 3 mol,% or less is preferable.

Next, a method for forming the shell will be described. Shell formation can be performed subsequent to completion of core particle formation. Alternatively, after forming the core particles, the core particles may be washed with water by a conventional 70-degree curation method, and gelatin may be added thereto for use as grains. In this case, by adjusting the amount of seed crystals, the size of the particles after shell formation and the core/shell ratio can be easily controlled.

The iodide content of the shell is 4m higher than the silver iodide content of the core.
It is necessary that the distance is 1% or more higher, and it is preferable that the distance is 10mol or more. Conventionally, it was difficult to chemically sensitize grains with a high silver iodide content on the outer surface to a level that allows them to be used in negative photosensitive materials, but this problem could be overcome by completely maintaining a clear double structure. Ta.

A clear double structure can be detected by the above-mentioned μ-hole X-ray diffraction method, and this means that the shell portion is composed of a uniform silver iodobromide mixed crystal. That is, even if the outer surface has a high silver iodide content, chemical sensitization can be effectively performed if the silver iodobromide mixed crystal is uniform.

To form a shell consisting of uniform silver iodobromide mixed crystals, a silver halide solvent such as ammonia, rhodan salt, thioureas, thioethers, amines, etc. is used to maintain a high solubility of silver halide. It is necessary to perform shell formation.

If you are careful and use Rodan salt, the pB at 73℃
It is necessary to carry out at rJ, j or more, pBrJ, preferably 4 or more, and particularly preferably pBrJ, g or more.

Further, even when ammonia, thiourea, or thioether is present all around, it is preferable to form a shell at pBrJ of 3 or more.

The temperature during shell formation is desirably high in order to increase the solubility of silver halide. The temperature is preferably 40°C or higher, most preferably 60°C or higher.

As a method for supplying iodine, bromine, and silver necessary for forming the shell S, various methods similar to those shown in the core formation method can be used, but a method in which they are added as silver iodobromide fine particles can be used. is particularly preferred. In this case, the silver iodobromide fine grains have a silver iodide content equal to or higher than the shell part of the target grain, and the grain size is 0.7 μm.
or less, preferably 0.06 μm or less, most preferably 0.03 μm or less. The rate of addition of the primary image particles is preferably around the dissolution rate of the added secondary image particles.

The aspect ratio of the particles obtained as described above is preferably j or less from the viewpoint of granularity. The improvement in graininess associated with a decrease in aspect ratio is particularly remarkable in such high surface iodine type particles according to the present invention, compared to the surface low iodine type particles outside the present invention.

The emulsions of this invention are typically spectrally enhanced.

Methine dyes are usually used as the spectral sensitizing dyes used in the present invention, and these include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Dyes are included. These pigments have basic differences f! Any nucleus commonly used for cyanine dyes can be used as the ff ring nucleus. That is, viroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole 1, oxazole nucleus, thiazole B, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and Nuclei in which aromatic hydrocarbon rings are fused to these nuclei, i.e.
Without indolenine, without benzindolenine, indole J
j;, without benzoxadol, with naphthoxadol core,
Benzothiazole core, naphthothiazole core, benzoselenazole core, benzimidazole core, quinoline core, etc. can be used. These nuclei may be In-doped 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, thiobarbyl nucleus, and the like can be applied.

The amount of aggravating dye added to silver halide emulsion 3141 cannot be unambiguously stated depending on the head of the additive and the amount of halide, but it is almost the same as the amount added by conventional methods. amount can be used.

That is, the preferred amount of aggravating dye added is halogenated jI
O per L-E-le, OOL~L Q O+*mol
'? ? Yes, more preferably 0. O1~10 +u
It is wo+.

The enhancing dye is added after or before chemical ripening.For the silver halide grains of the present invention, the enhancing dye is most preferably added during or before chemical ripening (for example, during grain formation or physical ripening). added to.

Along with aggravating pigments, pigments that do not themselves have spectral sensitizing effects or substances that do not substantially absorb visible light,
For example, the emulsion may contain a substance that exhibits hyperchromic enhancement.
Aminostyl compounds substituted with nitrogen-containing heterocyclic groups (for example, U.S. Pat. No. 2,933.390, U.S. Pat. No. 3,635,7)
No. 21), aromatic acid formaldehyde condensates (such as those described in U.S. Pat. No. 3,743,510), cadmium salts, azaindene compounds, etc., U.S. Pat. No. 3,615,613. No. 3, 6
No. 15,641, No. 3.617.295, No. 3,63
The combination described in No. 5,721 is particularly useful.

Silver halide emulsions are usually chemically sensitized.

For chemical sensitization, for example 11. Frisel (II.

Fr1eser) kW, Die Grundlagen der Fotografisien Brotsese Mitu Zilberhalogenidene (Die Grundlagen d
erPhotography Prozess
e mit Silberhalogeniden) (
Akademifsche Ferlags Geserschacht 1968
) The method described on pages 675 to 734 can be used.

Namely, sulfur enrichment methods using sulfur-containing compounds (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines) that can react with active gelatin or oxidants; reducing substances (e.g., stannous salts, reduction aggravation method using amines, hydrazine i-form, formamidine sulfinic acid, silane compounds); noble metal compounds (e.g. gold complex salts,
Pt.

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

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing capri during the manufacturing process, storage or photographic processing of the light-sensitive material, or for stabilizing the photographic fat. Azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (particularly nitro- or halogen compatibles); heterogenic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, Mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), mercaptopyrimidine neck; the above-mentioned heterocyclic mercapto compounds having a water-soluble group such as a carboxyl group or a sulfone group; Antifoggants such as compounds such as oxazolinthione; azaindenes such as tetraazaindenes (especially 4-hydroxy substituted (1,3,3a,7) tetraazaindenes); benzenethiosulfonic acids; benzenesulfinic acid; Many compounds known as stabilizers can be added.

The antifoggant or stabilizer is usually added once after the chemical aging, but more preferably it can be selected during the chemical ripening or before the start of the chemical ripening. That is, during the silver halide emulsion grain formation process, both during the addition of the silver salt solution and after the addition until the start of chemical ripening, during the chemical μ) formation (during the chemical ripening time, preferably within 50% of the start). more preferably up to 20% of the time).

The emulsion of the present invention can be used in photographic materials having any layer structure, regardless of whether the emulsion layer is IN or two or more layers.

A halogenated multilayer color photographic light-sensitive material using the emulsion of the present invention has a multilayer structure in which emulsion layers containing a binder and silver halide grains for separately recording blue, green and red light are superimposed, Each emulsion layer consists of at least two layers: a high-speed layer and a low-speed layer. Particularly practical layer configurations include the following.

+11 BH/BL10H/CL/RH/RL/5(
21BH/BM/, BL/GH/GM/GLRH/RM
/RL/S N configuration and +31 described in US Pat. No. 4,184,876
BH/BL/GH/RH/GL/RL/5RD-22
534, JP 59-177551, JP 59-1775
+41 BH/'GH/RH/BL/Gl, /RL/ described in 52 etc.
This is an N configuration of S.

Here, B is the blue-sensitive layer, G is the green-sensitive layer, R is the red-sensitive layer, H is the highest S cortex, M is the intermediate layer, L is the low-sensitivity layer, and S is the support. The recording of non-photosensitive layers such as layers, filter layers, interlayers, antihalation layers, and subbing layers is omitted.

Among these, preferred N configurations are (1), (2), or (4).

Also, (51BH/
BL/CL/GH/C, L/RH/RL/S +61 8H/BL/GH10L/CL/RH/RL/
rIJ configurations such as S are also preferred.

Here, CL is a multilayer effect imparting layer, and the pond is as described above.

Further, the high-sensitivity layer and the low-sensitivity layer having the same coloring property may be reversely arranged.

The halogen northern limit emulsion of the present invention can be applied to color light-sensitive materials as described above, but it can also be applied to other light-sensitive materials, regardless of whether the emulsion layer is one layer or multilayer, such as X-ray light-sensitive materials, black-and-white shadow light-sensitive materials, etc. It can be similarly applied to photosensitive materials, photosensitive materials for plate making, photographic paper, etc.

Additives for the silver halide grains of the present invention, such as binders, chemical sensitizers, spectral sensitizers, stabilizers, gelatin hardeners, surfactants, antistatic agents, polymer latex, matting agents, color couplers , ultraviolet absorbers, antifading agents, dyes, and supports for photosensitive materials using these emulsions;
There are no restrictions on the coating method, 8-light method, development processing method, etc., for example, Research Disclosure 17
Volume 6/Item 17643 (RD-17643),
Volume 187, item 18716 (RD-1871
6) and volume 225, item 22534 (RD-2
2534) can be referred to.

The descriptions of these research disclosures are shown in the rough table below.

Additive type 11017643 RD1871
6 1iD225341 Chemical sensitizer page 23
Page 648 Right column Page 24 2 Sensitivity enhancer Same as above 4 Brightening agent Page 24 Ultraviolet absorber 8 Dye image stabilizer Page 25 3
Page 2 9 Hardening agent Page 26 Page 651 left column
Page 28 10 Binder Page 26 Same as above 11
Plasticizer, IR, I lubricant Page 27 Page 650 Right column 14 Color coupler Page 25 Page 649
The color coupler used in Page 31 Akira Kinie is preferably diffusion-resistant by having a ballast i or being polymerized. A second-generation coupler substituted by AII degrouping is preferable because the amount of coated silver can be reduced.Furthermore, a coupler in which the color-forming dye has an appropriate expansion property, a non-color-forming coupler, or a coupler that undergoes a campling reaction is preferable. DIR couplers that release developer plate additives or couplers that release development accelerators can also be used.

A representative example of the yellow coupler that can be used in the present invention is an oil-protected acylacetamide coupler. A specific example is U.S. Patent No. 2,40
7.210, 2.875.057 and 3
, US Pat. No. 3,408,194, US Pat. No. 3,447,928;
No. 3,933,501 and No. 4,022゜62
Oxygen atom separation type yellow coupler described in No. 0, etc., or Japanese Patent Publication No. 5B-40739, U.S. Patent ¥J4
, No. 401,752, No. 4,326.024, RD
18053 (April 1979), British Patent No. 1,42
No. 5,020, West German Application Publication No. 2,219,917,
Same 2nd. No. 261.361, No. 2.329,587
Typical examples thereof include the nitrogen atom separation type yellow couplers described in No. 1, No. 2, 433.812, and the like. α-pivaloylacetanilide couplers have excellent color fastness, especially light fastness;
- A benzoylacetanilide coupler produces a 4 degree dark color.

Magenta couplers that can be used in the present invention include oil-protected indacylon or cyanoacetyl couplers, preferably pyrazoloazole couplers such as 5-pyrazolone and pyrazolotriazoles. The 5-pyrazolone coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group from the viewpoint of the hue and color density of the coloring dye. No. 2゜343.703, No. 2,600.788, No. 2
．． No. 908.573, same No. 3. 062. No. 653,
3,152.896 and 3゜936.01
It is stated in issue 5 etc. As a leaving group for a two-equivalent 5-pyrazolone coupler, U.S. Pat.
No. 9 or the nitrogen atom leaving group described in U.S. Pat.
Particularly preferred are the arylthio groups described in No. 351,897.

Further, the 5-pyrazolone coupler having a ballast group described in European Patent No. 73,636 provides a satisfactory color density.

As a pyrazoloazole coupler, U.S. Patent No. 3,
061,432, preferably pyrazotff (5,1-C)(1,2,4) as described in U.S. Pat. No. 3,725.067
Triazoles, Research Disclosure 242
20 (June 1984) and JP-A-60-3355
Pyrazolotetrazoles and research described in No. 2
Disclosure 24230 (June 1984) and JP-A No. 60-43659, the pyrazolopyrazoles are mentioned in U.S. Pat. 500°630
The imidazo(1,2-b)pyrazoles described in US Pat.

Cyan couplers that can be used in the present invention include oil-protected naphthol couplers and phenolic couplers, preferably the naphthol couplers described in U.S. Pat. No. 2,474°293, and preferably U.S. Pat.
, No. 212, No. 4゜146.396, No. 4,22
Typical examples include two-equivalent naphthol couplers of the oxygen atom elimination type described in No. 8,233 and No. 4,296,200. Specific examples of phenolic couplers include U.S. Pat. No. 2,369,929 and U.S. Pat.
No. 01.171, No. 2,772,162, No. 2.
No. 895,826, etc. Humidity and temperature robust cyan couplers are preferably used in the present invention, exemplified by U.S. Pat. No. 3,772.
．． Phenolic cyan coupler having an alkyl group greater than or equal to ethyl group in the meta-position beyond the phenol described in US Pat. No. 2,772,162, US Pat. No. 3.75
No. 8,308, No. 4,126,396, No. 4,3
No. 34,011, No. 4.327゜173, West German Patent Publication No. 3,329,729 and European Patent No. 121,
2,5-diacylamino ft described in No. 365 etc.
A Phenolic Coupler and U.S. Pat. No. 3,446,
No. 622, No. 4,333,999, No. 4.451
, No. 559 and No. 4,427,767, etc., which have a phenylureido group at the 2-position and an acylamino group at the 5-position. Patent application No. 59-93605, No. 59-264277
Cyan couplers in which a sulfonamide group, an amide group, or the like is substituted at the 5-position of naphthol described in No. 1 and No. 59-268135 also have excellent fastness of colored images and can be preferably used in the present invention.

In order to correct unnecessary absorption in the short wavelength range of dyes generated from magenta and cyan couplers, it is preferable to use colored couplers in combination with color negative materials for shadowing, as disclosed in U.S. Pat. No. 4,163.670 and Tokuko Showa 5
7-39413, or U.S. Pat. No. 4.0.04,929, U.S. Pat.
Typical examples include the magenta-colored cyan coupler described in No. 68.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Examples of such blur couplers include magenta couplers in U.S. Pat. No. 4,366.237 and British Patent No. 2,125,570.
Also, European Patent No. 96゜570 and West German Application No. 3
, 234,533 describes specific examples of yellow, magenta or cyan couplers.

The dye-forming couplers and special couplers described above may form polymers of dimers or more. Typical examples of polymerized dye-forming couplers are described in U.S. Pat. No. 3,451,82.
No. 0 and No. 4.0130°211. Specific examples of polymerized magenta couplers include British Patent No. 2,102.173 and U.S. Patent No. 4.367.28.
No. 2, Japanese Patent Application No. 60-75041, and No. 60-11
No. 3596.

The present invention may also include a coupler that releases a development inhibitor upon development, a so-called D[R coupler.

As a DIR coupler, for example, U.S. Patent Tube 3°227
．． Those that release heterocyclic mercapto type development inhibitors as described in No. 554, etc.; IC!, as described in Japanese Patent Publication No. 58-9942, etc. A so-called colorless DIR coupler that releases a benzotriazole derivative as a development inhibitor; a so-called colorless DIR coupler described in Japanese Patent Publication No. 51-16141, etc.; Release of nitrogen heterocyclic development 1rtl inhibitor; U.S. Patent No. 4,24
8,962 and JP-A-57-56837, which release a development inhibitor with an intramolecular nucleophilic reaction after separation; JP-A-56-114946, JP-A-57-4542
No. 34, No. 57-188035, No. 5B-98728
No. 5B-209736, No. 58-2097: Development inhibitor by electron transfer tds via a conjugated system after separation as described in No. M, No. 58-209738, No. 58-209739, No. 58-209740, etc. JP-A-57-151944 and JP-A No. 58-2179
Diffusive developing plate in which the development inhibitor is deactivated in α, as described in No. 32, etc.: one that releases the inhibitor; Japanese Patent Application No. 59-38
263, No. 59-39653, etc., which release a reactive compound and generate a development inhibitor by reaction in the film during development, or deactivate the development inhibitor. Among the DIR couplers mentioned above, the one more preferable in combination with the present invention is disclosed in Japanese Patent Application Laid-open No. 5
Developer deactivated type represented by No. 7-151944; U.S. Pat.
Timing type represented by No. 34; patent application 1986-396
The reaction type is represented by No. 53, and among them, the preferred ones are those disclosed in JP-A-57-151944 and JP-A-58-2.
No. 17932, Japanese Patent Application No. 59-75474, No. 59-8
No. 2214, No. 59-82214 and No. 59-90
438 and the like, and a reactive DIR coupler described in Japanese Patent Application No. 59-39653 and the like.

In the light-sensitive material of the present invention, a compound that releases a nucleating agent, a development accelerator, or a precursor thereof (hereinafter referred to as "development accelerator, etc.") in a stroke pattern during development can be used. A typical example of such a compound is British Patent No. 2,0
97,140 and 2.131 188, and is a coupler that releases a development accelerator etc. by a coupling reaction with an oxidized product of an aromatic primary amine developer, that is, a DAR coupler.

It is preferable that the development accelerator etc. released from the DAR coupler have adsorption properties to silver halide.
No. 638 and No. 59-170840. DAR couplers that form an N-acyl substituted hydrazine neck having a monocyclic or fused heterocycle as an adsorbent group, which is detached from the photocoupling active site of the photographic coupler with a sulfur atom or a nitrogen atom, are preferred for the frame. Specific examples of couplers are described in JP-A-60-128446.

Specific examples of high precipitate solvents used for dispersing color couplers include phthalate esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, etc.), phosphoric acid, or phosphonic acid. Acid esters (triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate)
), ) IJ-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexyl phenine bosphonate, etc.), benzoic acid esters (2-ethylhexyl benzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amide neck (diethyldodecaneamide, N-
(tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (dioctyl azelate, glycerol tributyrate, isostearyl lactate, octyl citrate, etc.), aniline m1 (N,N-diptyl-2-butoxy-5-t@rt-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.), and the like. In addition, as an auxiliary solvent, the boiling point is about 30°C or higher, preferably 5°C.
An organic solvent having a temperature of 0° C. or more and about 160° C. or less can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, and dimethylformamide.

Suitable supports that can be used in the silver halide photographic emulsion of the present invention are described, for example, in RD, No. 17643, page 28, and in m1B7L6, page 647, right column to page 648, left column.

The binder used in the silver halide emulsion to which the present invention is applied is preferably gelatin, but in addition to gelatin, derivative gelatin such as phthalated gelatin, dextran, cellulose derivatives, polyvinyl acetate, polyacrylamide, polyvinyl alcohol, etc. used.

Examples of gelatin hardening agents include active halogen compounds (
2,4-dichloro-6-hydroxy-1゜3.5-triazine and its sodium salt, etc.) and active vinyl compounds (1,3-bisvinylsulfonyl-2-propatol, 1,2-bis(vinylsulfonylacetamide, etc.) ) Vinyl polymers having ethane or vinylsulfonyl groups in their side chains) are preferred because they quickly harden hydrophilic colloids such as gelatin and provide stable photographic properties.

N-carbamoylpyridinium salts [(1-morpholinocarbonyl-3-pyridinio)methanesulfonate, etc.)
Yaheroamidinium salts [(1-(1-chloro-1-pyridinomethylene)pyrrolidinium 2-naphthalenesulfonate, etc.) are also excellent in their fast curing speed.

The color photographic light-sensitive material using the silver halide photographic aperture 'El of the present invention is described in RD, No. 17643, pages 28-29, and No. 17643, pp. 28-29. Development processing can be carried out by the usual method described in 651 left column to right column of H 18716.

A color photographic light-sensitive material using the silver halide photographic emulsion of the present invention is usually subjected to a water washing treatment or a stabilization treatment after development, bleach-fixing or fixing treatment.

In the washing process, two or more tanks are generally used for countercurrent washing to save water. A representative example of the stabilization treatment is a multistage countercurrent stabilization treatment as described in JP-A-57-8543 instead of the water washing step.

Coloring T! used in the development process of the photosensitive material of the present invention! 1. The developing solution is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but
p-phenylenediamine compounds are preferably used,
Typical examples include 3-methyl-4-amino-N, N-
Diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-
4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides or p-)toluene Examples include sulfonates. Two or more of these compounds can be used in combination depending on the purpose.

The color developer may be a pH 311i agent such as alkali metal carbonates, borates or phosphates, bromide salts, iodide salts, benzimidazoles, benzothiazole or mercapto compounds; It generally contains antifoggants and the like. Also, if necessary, hydroxylamine, diethylhydroxylamine,! ! ! Various preservatives such as hydrazine sulfate, phenyl semicarbazides, triethanolamine, catechol sulfonic acids, triethylenediamine (1,4-diazabicyclo[2°2.2]octane), ethylene glycol, diethylene glycol, etc. JRi
Benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, fogging agents such as sodium poron hydride, 1-phenyl-3
- Auxiliary developing agents such as pyrazolidone, viscosity-imparting agents, various chelating agents such as aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids, such as ethylenediaminetetraacetic acid and nitrilotriacetic acid. , diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid,
1-Hydroxyethylidene-1,■-diphosphonic acid, nitrilo-N,N,N-)rimethylenephosphonic acid, ethylenediamine-N,N.

Representative examples include N',N'-tetramethylenephosphonic acid, ethylene glycol (0-hydroxyphenylacetic acid), and salts thereof.

Further, when performing reversal processing, black and white development is usually performed and then color development is performed. This black and white present i3. The liquid contains dihydroxybenzenes such as hydroquinone, 1-phenyl-3
Known black and white development strategies such as 3-pyrazolidones such as -pyrazolidone or aminophenols such as N-methyl-p-aminophenol can be used alone or in combination.

The p) of these color developing solutions and black and white developing solutions is 9 to 12.
It is common that The amount of replenishment of these developing solutions depends on the color photographic light-sensitive material to be processed, but it is generally less than 31 per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher,
It can also be less than C1+1. When reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing I with the air.
Furthermore, the amount of 1ili can be reduced by using means for suppressing the Wa of bromide ions in the developer.

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

The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process), or separately (bleach-fixing process), or in order to speed up the process, it may be possible to perform a bleach-fixing process after the bleaching process. Depending on the purpose, treatment may be carried out in consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment. Examples of bleaching agents include iron (■), Kobal) (m
), chromium (■), compounds of polyvalent metals such as copper (II), peracids, quinones, nitro compounds, etc. are used.

Typical bleaching agents include ferricyanide 51 dichromate; mono(III) or cobalt(III) staged complex salts such as ethylenediaminetetraacetic acid, diethylenetriaminepentafertic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1. Aminopolycarboxylic acid Mlff such as 3-diaminopropanetetraacetic acid, glycol etheramine tetraacetic acid, or complex salts of citric acid, tartaric acid, malic acid, etc.; persulfates; bromates; permanganates; nitrobenzenes, etc. may be used. I can do it. Of these, ethylenediaminetetra vinegar! Aminopolycarboxylic acid iron (I[[) complex salts and persulfates, including 2 iron (III) complex salts, are preferable from the viewpoint of rapid processing and environmental pollution prevention, and aminopolycarboxylic acid iron (m) complex salts are suitable for use in bleaching solutions. It is also particularly useful in bleach-fix solutions. The pH of one bleaching solution or bleach-fixing solution using these aminopolycarboxylic acid iron(I[I) complex salts is usually 5.5 to 8, but in order to speed up the processing, the pH is lowered. You can also do that.

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

Specific examples of bleach accelerators for use in
, No. 290,812, JP-A-53-95.630, Research Disclosure Ma 17,129 (197
Compounds having a mercapto group or disulfide bond as described in J. P. 1989); thiazolidine derivatives described in JP-A-50-140.129; U.S. Patent No. 3.706;
Thiourea V', a conductor, described in No. 561;
Iodide salts described in No. 235; West German Patent No. 2.748.
The polyoxyethylene compound described in No. 430; the polyamine compound described in Japanese Patent Publication No. 45-8836; bromide ion, etc. can be used. Among these, compounds having a mercapto i or disulfide group are preferable from the viewpoint of having a large promoting effect, and are particularly described in U.S. Pat. Preferred are the compounds described in U.S. Pat. No. 4,552.
The compounds described in No. 834 are also preferred. These bleaching accelerators may be added to the photographic material. 1. These bleaching accelerators are particularly effective when bleach-fixing color light-sensitive materials for maximum shadows. .

Examples of fixing agents include thiosulfates, thiocyanates, 1,000-onythyl compounds, thioureas, and multiple iodide salts, but thiosulfates are commonly used, especially ammonium thiosulfate. Most widely used. ? g
Hakusei M? As the preservative for &, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred.

The silver halide color photographic light-sensitive material of the present invention is subjected to a water washing and/or stabilization step after the 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 (the number of stages), the replenishment method such as countercurrent or forward flow, and other conditions of each plate. Can be set over a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is
urnalo(the 5ocieLy or Mot
ion Picture and Television
nEngrneers Volume 64, P, 24B-253 (
It can be determined by the method described in May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will grow twice and the generated suspended matter will adhere to the photosensitive material. In the processing of the color photosensitive material of the present invention, problems such as the following occur:
The method of reducing calcium ions and magnesium ions described in Japanese Patent Application No. 131.632/1988 can be used very effectively. Also, JP-A-57-8. 54
Isothiazolone compounds described in No. 2, thiabendazole, chlorine-based disinfectants such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., Doroguchi 1! ``Chemistry of anti-Z repellents'', Hygiene Technology Association ``Sterilization of microorganisms, sterilization, and anti-mildew technology'', Japan Anti-Mold and Antifungal Society Hato ``Encyclopedia of dent-proofing agents''
It is also possible to use the fungicides described in .

The pH of the washing water in the processing of the photosensitive material of the present invention is 4-
9, preferably 5-8. The washing water temperature and washing time can also be set depending on the characteristics of the photosensitive material, its use, etc., but generally it is 20 seconds to 10 minutes at 15-45°C, preferably 20 minutes.
The range of 30 seconds to 5 minutes at 5-40℃ is i! ! translated. Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water. In such stabilization treatment, all known methods described in JP-A-57-8.543, JP-A-58-14.834, and JP-A-60-220.345 can be used.

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

It is also possible to add various botanical agents and antifungal agents to this stabilizing bath.

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

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate a color developing agent, it is preferable to use each ring precursor of the color developing agent. For example, U.S. Patent No. 3,342.59
Indoaniline compound described in No. 7, No. 3,342,
No. 599, Research Disclosure 14.135
Schiff base type compounds described in No. 0 and No. 15,159,
Aldol compounds described in U.S. Patent No. 13.924, metal salt complexes described in U.S. Pat.
Examples include urethane compounds described in No. 135.628.

The silver halide color light-sensitive material of the present invention may contain 11 1-phenyl-
Typical compounds that may contain 3-pyrazolidones are disclosed in JP-A-56-64,339 and JP-A-57-144.54.
No. 7, and No. 58-115.438.

The various processing solutions used in the present invention are used at temperatures of 10°C to 50°C. a Normally, the temperature is 33°C to 38°C, but higher temperatures can be used to accelerate processing and shorten processing time, or lower temperatures can be used to improve image quality and stability of processing solutions. can be achieved. Furthermore, for the purpose of improving the stability of photosensitive materials, a treatment using cobalt intensification or hydrogen peroxide fni force as described in German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be carried out.

The present invention will be further explained with reference to Examples below.

Example 1 Emulsion/(Pure bromide matrix particles) 0.0 nM potassium bromide was added to a 3-t% gelatin solution // while thoroughly stirring, using a double jet method. .39M silver nitrate bath solution and Q, 39M potassium bromide solution are added /jcc for 73 seconds. During this time, the gelatin solution! ;O”C.

was maintained. After the heavy addition, the temperature was raised to 73°C.

After completing the above-mentioned stage addition, 0.117M silver nitrate bath solution was
OCC was added over a period of 7 minutes.

From another 70 minutes to 60 minutes/! Of silver nitrate was then added at an accelerated flow rate (end flow rate 77 times the start rate). During this 60 minute pBr was maintained at 3°OO.

Thereafter, the emulsion was cooled to t-j j'C and 70%
Cleaned by curing method and maintained at pH 6.0 at ≠0°C.
3. After adjusting the pAgl to 6, store it in a cool, dark place. The male tabular grains account for 7% of the tabular grains, and the coefficient of variation thereof is 76%. Furthermore, this particle is D
The circle is / ,, 2.2 μm, and the average thickness is 0
．． ! ≠μm. Data regarding particle size was obtained from electron micrographs.

Emulsions 2 to 10 (grains with shells with high silver iodide content) Emulsions/1 (This is A g B r grain *i, 2 oy
After adding distilled water/λ to (containing), the potassium thiocyanate aqueous solution t'fc shown in Table/ is 3.6-cythyl,
Then add octanediol. This solution i 73 °C
The PBr values shown in Table 1 were adjusted using a silver nitrate aqueous solution and a potassium bromide aqueous solution. After this 0. Riza M
When the concentration of silver nitrate aqueous solution, iodide ion, and bromide ion is 0. ．． 291AM and 0.611. Igocc7) rhe shell was formed using a controlled double jet method with an aqueous halogen solution.

During this period, the law was set so that PBr would have the values shown in Table 2.

This emulsion was washed by the usual 70°C curing method and inert gelatin jO was added to pM+, jb at ≠θ°C.
Adjust so that pAgl is A, and make emulsion 2-10.

Emulsion // (Grains with pure silver bromide shell) For comparison, the halogen aqueous solution used to form the shell was O07.
Emulsion 7 was prepared in exactly the same manner as emulsion j, except that it contained only potassium bromide at a concentration of , 5-M.

The prescription core/shell ratio of these emulsions (the ratio of the amount of silver in the core to the amount of silver in the shell) is j, and the silver iodide content in the shell part according to the prescription is 30 monch (however, (excluding l and l/f). 42 shows the ratio of peak intensities obtained by X-ray diffraction and the silver iodide content of the silver iodobromide portion of the shell.

The peak intensity ratio referred to herein is the ratio of the peak intensity shown by the silver iodobromide part of the shell to the peak intensity shown by the pure silver bromide part of the core. BROAD in the table indicates a case where the peaks are not separated, and is an example of a particle that does not have a clear layered structure. Therefore, the silver iodide content of the shell portion could not be determined by the X-ray diffraction method, and the X-ray diffraction patterns of emulsions J and j are shown in grain diagram 1 contained in nine emulsions 2 to /I.

The size determined by electron micrograph is D circle /,
,2/μm to/,,23μm and the thickness is 0゜2μm
It was 0.27 μm from m.

The emulsion of 1H11 above was optimally chemically sensitized using sodium thiosulfate and potassium chloroaurate, and the following samples were prepared and processed.

(a) In the case of black and white development processing After the above chemical sensitization, 100y of each emulsion /~//
The mixture was dissolved at ℃ and the following steps 1 to 2 were added to the solution while stirring.

■ Guhydroxy-6-methyl-/, 3.3a, 7-
Citrazaindene 3% 2cc ■C17)135-0-(C)12CHO)2. −
) 12% j,, 2ce Apply the surface protective layer coating solution at 44'O℃ according to the following.
Add the mixture one by one while stirring to prepare a solution.

■ lμtizelatin aqueous solution! A, gl ■ Polymethyl methacrylate fine particles (average particle size 3.0 μm) 3.97 ■ Emulsion gelatin 70% g, J Geta C) 12COOC) 12C) i (C2) 1 s) C4
)19NaU3B-C)icUUc)i2C)i(C2
H5) C4Hg70.6 ~ ■ h2o g♂, fcc da, 3% 3 cc A cellulose triacetate film support was prepared by the simultaneous pressing method together with the next emulsion coating solution obtained as above and the coating solution for surface protective layer. Each layer was coated on top so that the volume ratio at the time of coating was 703.

Coated silver t is 3. /9/-. 200 fluxs with a light source with a color temperature of 213μ' for these samples.
After applying a wet exposure for 1 second, it was developed for 7 minutes at !0°C with the following developer D-76, fixed with fixer F-/, washed with water, and dried.

[Developer D-76] Metol 2-sodium sulfite 100 tahydroquinone
39 Borax! H20/
,! 39 Add water/2 [Fixer F-/] Ammonium thiosulfate Cooo, oy Sodium sulfite (anhydrous) 20.09 Boric acid
r, oy ethylenediaminetetraacetic acid di o, ip aluminum sodium acid is, oy sulfuric acid
λ, O glacial acetic acid
22. C# Add water to make /2.

(The pH is adjusted to ≠, 2.) (0) In the case of color development processing, the emulsion and protective layer are coated on a triacetyl cellulose film support, which is provided with an undercoat layer.

The structure of each layer is as follows.

(1) Emulsion layer/emulsion/~ll (coated silver amount 2,.2 X/Q-2
mob/false 2) ・Coupler (i, j×io mol/rr?)a ・Tricresyl phosphate (/,lOP/Wt″) ・Gelatin (,2,3oy/rr?)
(2) Picking machine j- ・2. t-dichlorotriazine-6-hydroxy-5
-Triazine sodium triwam salt (0,0zap/i) ・Gelatin (/, goy/rrt”)
After drying, give a sensitometric evening light exposure for 7770 seconds and perform the following Fuji CN/b treatment.

(Fuji CN-76 processing) The development processing used here was performed at 31° C. under the following conditions.

1. Color development 2 minutes 4 tons
J seconds 2, white washing ・・・・・・・・・ 6 minutes 30 seconds 3, washing with water ・・・・・・・・・ 3 minutes/j seconds washing ・・・・・・・・・・・・・・・ 6 minutes 3
0 seconds, wash with water ・・・・・・・・・ 3 minutes/
j seconds 6, stable ・・・・・・・・・ 3 minutes/
The composition of the treatment liquid used in each step is as follows.

Color developer sodium nitrilotriacetate /, OP sodium sulfite, oy sodium carbonate
30.0 Potassium Bromide
/, ≠2 hydroxylamine sulfate
J, 4t7μm (N-ethylhe β-hydroxyethylamino)-comethyl-aniline sulfate ≠, 3 water added 11 bleach solution ammonium bromide /60. Op ammonia water (2g%) 23.0ml ethylenediamine-tetraacetic acid sodium iron salt /30 F glacial acetic acid /Hiro Go water added
/L fixer sodium tetrapolyphosphate 2. OF Sodium sulfite da,oy ammonium thiosulfate (70%)/73. Otd Sodium Bisulfite Wam
≠, add 6y water
l Lambda stabilized formalin ♂, Oyd water added 12 The results of these sensitometry are shown in Table 2 as follows. As is clear from Table 2, although the grains according to the present invention have a high silver iodide gold content of 7 Km in the shell portion, they have a high W&D kW that is equal to or higher than that of pure silver bromide grains.

table/ Example 2 Emulsion 1.2 (silver iodobromide matrix grains) The following molten g was manufactured by FA.

Next, keep the flame at 30"C and add B and C while stirring the friend's solution.
g, and 73CC each added using the gold double jet method. After adding foil, heat to 73°C and add 220cc of 70% by weight gelatin solution.
Added an additional element.

Next, solution B was added over a log of 5 ccio minutes. After a further 10 minutes, 600 cc of liquid D and liquid E were added using a controlled double jet method for 60 minutes. At this time, the flow rate of liquid D is set at a different speed so that the flow rate at the end is twice the flow rate at the start.

The flow rate of the 7tE solution was adjusted so that the pBr of the system was 2.3.

After this, the emulsion was cooled to 33°C, washed by a conventional flocculation method, and the pH6.j, pAg
Adjust to J' and then store in a cool, dark place. The tabular grains accounted for 9% of the tabular grains, and the coefficient of variation was 77. Furthermore, this particle ViD circle 7>E/, 2≠μm, and the average thickness Ir1o
, 2 μμm. Data regarding particle size were determined from electron micrographs. Also, the silver iodide content is 10m
oλchi.

Emulsion-/3 (fine grain emulsion for shell formation) inert gela f
＞/99 and KBr (10%) // and Jcc were dissolved in distilled water 11 and used as solution A.

Prepare a 7715M silver nitrate aqueous solution and use it as Solution B.

Furthermore, KBr//2:l and KI3ri1 were dissolved in distilled water/2 to prepare a solution C. While keeping liquid A at 33℃,
The liquid and C liquid are controlled and then the double jet method is used to make Tsuka friends. The amount of B liquid added was 300CC.

After washing this emulsion using the conventional 70 curation method,
Inert gelatin j Yyf edge, ph6 at tO℃.
17. Emulsion 1 was prepared so that pAgl was 0.
I got a 7. Emulsion/7 is 1! According to the photograph, it was fully formed with an average diameter of 0.0 μm. The stiffening content is 29 mof1%.

Emulsion/μ Emulsion/2 After adding distilled water/2 to 13391, potassium thiocyanate water gg, (?N) was added.

This solution 'i7j at pBr3. /3 using a silver nitrate aqueous solution and use it as Solution A.

On the other hand, emulsion 13 Hiroj-no (containing 266 moles of complex 00) was dissolved in JQ''c and cooled to liquid A for ≠j minutes.

During this time, liquid A was kept at 75°C, and after the addition of t0,
After aging for 70 minutes, it was washed using the curation method. Add inert gelatin jQy, adjust pH to 4tO℃,
≠, pAg, r, was adjusted to 6 to obtain an emulsion /≠.

The prescription core/shell ratio of emulsion/≠ is 1, and the prescription shell silver iodide content is 2Qmof1%. −
The ratio of the shell peak intensity to the core peak intensity by 10,000Xa diffraction is //2. ls, and the silver iodide content of the shell was ll1moλchi.

The resulting particles had a D-length of 23 μm and a thickness of 0.36 μm.

Emulsion/J (comparative emulsion) Distilled water/λ was added to Emulsion/l 133y, and then an aqueous solution of potassium thiocyanate (2N) was added.

This solution was heated at 73°C to pBr3. /3 using an aqueous iron nitrate solution. This was followed by addition of a 0.92 fM aqueous potassium bromide solution and a 0.92 fM aqueous solution of nitric acid using a fully controlled double jet method.

The purity of the aqueous nitric acid solution added was -77 μcc. The obtained grains were tabular grains with a D-circle of /, 22 μm and a thickness of 0.37 μm.

The emulsion was optimally chemically sensitized using 3-ethyl-j-benzyritine rhodanine and potassium chloraurate, and ≠-hydroxy-6-methyl-/, 3.3a, 7-tolazaindene was added. 3y/? It was coated on a polyethylene terephthalate support so that the amount of silver was ♂. Next, for these samples, a tungsten light source was applied with an interference filter of ≠/nm to 7710
After exposure to blue light for 2 seconds, the film was developed (20° C.≠minutes) with the following developer D-/, fixed with fixer F-/, and after 7'C, washed with water and dried.

[Developer D-7] /-phenyl-3-pyrazolidone o,syhydroquinone,2o,oyethylenediaminetetraacetic acid dino,olsodiumpotassium sulfite o,oyboric acid≠,Qpotassium carbonate ro,oy sodium bromide
j,oy diethylene glycol
30. Add water to make /λ. (pH is 7
Adjust to 0.0. ) As a result of sensitometry, when emulsion /j was set to KFKkloo, the N&thigh of emulsion /q was /3/.

′! Takafuri density is emulsion 7≠0.10, so emulsion/3
is 0. //Met.

As described above, the grains according to the present invention achieved high sensitivity and low fog despite the high silver iodide content in the shell portion.
Yet another surprising effect is that the dye sensitivity is significantly improved compared to grains with a low iodide content in the shell (lower than the core). An example is shown below.

Example 3 Emulsion! , 7, //, /≠, /3 3-Ethyl-j-penzylidene rhodanite was optimally chemically increased using potassium chloraurate. I'm a friend and the W below is
Dye I was added immediately before or after total chemical sensitization, or was not added at all.

The amount of dye added was the saturated adsorption amount to the grains in each emulsion, and the saturated N adsorption amount was determined by the Kubelkamunk method.

Example after the above chemical sensitization! The emulsion layer and surface storage layer were coated using the method described in .

For these samples, an interference filter that transmits the source μ/Fnm (half width/!nm) from a light source with a color temperature of 2gj≠ and an 8C32 Fuji filter that transmits wavelengths longer than 20nm are used. going back to 7
Each photo was exposed to blue and negative blue for 710 seconds. This was followed by Kodak D7A treatment as described in Examples.

The results of sensitometry are shown in Table 3. The alphabet after the Ibaranaka emulsion number indicates that A is the case where the dye is not added, B is the case where the dye is added before chemical sensitization, and C is the case where the dye is added after chemical sensitization. Blue sensitivity is 1t-h2i
This is a relative value when it is set to oo. In the present invention, the loss of fixation sensitivity due to dyes is significantly improved. At this time, the minus blue sensitivity is significantly higher than that of a specific soft emulsion (minus blue sensitivity is a relative value when taken as //-B''f (100)).

Table 3 Example ≠ On a subbed cellulose triacetate film support,
Multilayer color g+ consisting of each l- having the composition shown below
Samples 10/~103ft of material were prepared.

(Composition of photosensitive layer) Coating amount is halogen ratio value, colloidal silver and coupler are silver P/rr? The amount expressed in units is expressed as the number of moles per mole of halogenated group in the same layer for sensitizing dyes.

1st layer: antihalation layer black colloidal silver silver coating t O,, 2 gelatin )・2UV-to・/ UV-uO・1 Cpd-/ 0.
03Solv-/0.0
/5olv-,20,0/5olv-30,Og λth layer: Intermediate layer fine grain silver bromide (equivalent sphere diameter 0.07μ) Coating amount 0. /3 Gelatin /, 0cpa-
,z O,2 3rd layer: 1st
Red-sensitive emulsion 1 Silver iodobromide emulsion (A g I / Q, Q molten, internal high Ag I type, equivalent sphere diameter 0.7μ, coefficient of variation of equivalent sphere diameter /IA%, /prohedral grain) Silver coating amount 0 ．． ．． 2A Silver iodobromide emulsion (AgI Hiro, 0 molti, internal high AgI type, equivalent sphere diameter 0. Hiroμ, coefficient of variation of equivalent sphere diameter, 22%, l-prohedral grains) Silver coating amount 0.2 Gelatin /, 0ExS-
i < t, 5xtO mol ExS-2/
, jx/ 0-' mole ExS-30, Hiro X no θ mole ExS-≠ 0.3X10 mole ExC
−/0.33
ExC-20,00 ExC-30, 0,23 ExC-60, / I/L 2nd ≠ 2nd layer 2 red-sensitive milk ax j layer silver iodobromide emulsion Threshold distribution amount 0. ! ;3; Gelatin 0.7Ext-/ ExS-2 ExS-3 ExS-≠ ExC-10,01 EXC-J o, osEx
C-40,10 J-th layer: Third red-sensitive emulsion layer Silver iodobromide emulsion Silver coating amount 0.7 Gelatin
0.6xS-t ExS-, I ExS-3 ExC-≠ 0.0
7ExC-JO
,01°8o1v-/
0. /,2Solv-,20,/2 6th layer: Intermediate layer gelatin //0cpa-
≠ 0.7 7th layer 2nd glaucoma emulsion layer Silver iodobromide emulsion (AgIlo, 0 molti, internal high AgI type, equivalent sphere diameter 0.7μ, coefficient of variation of equivalent sphere diameter / Hirochi, / prohedral Grains) Silver coating amount 0.2 Silver iodobromide emulsion (AgIIA, Q Morti, internal high AgI type, equivalent sphere diameter 0.Hiroshiμ, coefficient of variation of equivalent sphere diameter 22%, lIAhedral grain) Silver coating amount o, i gelatin /, λExS-j
Exlo 'Ex S -
1r, 2X/0-'E
xS-7/x10-' ExM-10, Hiroshi BxM-20,10 ExM-! ; 0.038
o1v-/0.2 g layer:
Second green-sensitive emulsion layer silver iodobromide emulsion Silver coating amount 0. ≠gelatin
0.3! xS-j ExS-6 ExS-7 ExM-/ 0.0YEx
M-30,0/5olv-/0. /! No. 72: Middle layer gelatin O1! IO layer: 3rd green-sensitive emulsion layer Silver iodobromide emulsion Silver coating amount /, 0 gelatin
0. ♂xS-j ExS-A ExS-7 ExM-g O,011E
xM-30-0/ ExC-p 0.00!5o
lv-/0.2 1st/layer: Yellow filter layer Cpd-30,03; Gelatin 0.jSolv-
/ 0. /12th layer: Intermediate layer gelatin 0. jCpd-,
20 / 13th layer: 1st blue-sensitive emulsion layer Silver iodobromide emulsion (AgI 10 molti, internal high iodine plastic, equivalent sphere diameter 0.7μ, coefficient of variation of equivalent sphere diameter /≠CH, l-prohedral grains) Silver Application amount 0. / Silver iodobromide emulsion (AgI, 0 mole, internal high iodine type, equivalent sphere diameter O1 Hiroμ, coefficient of variation of equivalent sphere diameter, 2λ, / Q-hedral grain trowel coating fi-0,0! Gelatin /, OExS-
g 3x10 'ExY-
/ 0. J3ExY-20
,02 Solv-/0. /J 1st
Hiro layer: 2nd blue-sensitive emulsion layer Silver iodobromide emulsion (AgI / 0 mol, internal high AgI type, equivalent sphere diameter /, 0 μ, variation in equivalent sphere diameter 76%, /≠hedral grains) Silver coating Amount 0. / Tagelatin 0.3ExS-g
ノ×10 'ExY-
/ 0.22Solv
-/ 0.07 1st J layer: Intermediate layer fine grain silver iodobromide (AgIλ morti, uniform type, equivalent sphere diameter 0.73μ) Silver coating amount 0.1 Gelatin 0.36 1st B layer: 3rd blue-sensitive emulsion Layered silver iodobromide emulsion (AgIl≠, Q mole, high AgI type, equivalent sphere diameter/, 3μ, coefficient of variation of equivalent sphere diameter 2♂chi, plate-like grains, diameter/thickness ratio J, O) Silver Application amount /, 0 Gelatin 0.3ExS-za /,! ×10-'ExY-10.2 Solv-/ 0.07 17th
Layer: 1st protective layer gelatin /-1UV-/
o, 1UV
-, zo, λ 8o1v-/
0.0/5olv-,!
0.0/7th g layer: 2nd protective layer fine grain silver bromide (equivalent sphere diameter 0.07μ) coating amount 0.7g gelatin 0.7 polymethyl methacrylate particles (diameter i, jμ) 0. ．． 2W-1
0,02) 1-10. μ Cpd-j /, as the emulsion for the 0th μ layer, the 5th layer, the g layer, and the io layer, sample 10/
In Example-7, emulsion/16 was used, in sample IO-, the same emulsion/114 (invention) was used, and in sample 103, the same emulsion was used (
This invention) can be used by friends.

Samples 102 and 103 had extremely good sensitivity and graininess compared to / (7/).

The structural formula of the cooling agent used in each sample is shown below.

V-ix / y = 7 / j (Todohi) UV-x ExM-3 ■ ExC-3 (9(tl ExC-/ (ilU4M9sushi+,,INM tJt;ki2
ul-126) to i2 (J(JMxC-2 H2 ExC-Hiro0 (n11., :xzH2s
xC-j C1C12)1 25Ex/H Jujube (weight ratio) Average molecular weight Hiroo, oo.

ExM-2 α Ex hi-HiroExM-j α ExY-/ExY-,2 ExS-/ExS-2 (CH2)4 dlJ3Na ExS-J ExS-HiroExS-j ExS-A C2H5 ExS-1 ExS-7 (Shi H2) 4 Gori 3A Solv-/ 5olv-λ Solv-J Cpd-/ cpa-2 Cpd-3 CH3 cpa-Hiropct-j H VV--/ C3F17SO2NHCH2CH2CH20CH2CH
2NO(CH3)2CH2=CH8O2CH2CONH
-7H2CH=CH8O□CH2C0NH-CH2 Preferred embodiments of the invention are as follows.

1. In a photographic light-sensitive material having at least seven silver halide emulsion layers on a support, 30% or more (projected surface area) of the halogenated @ grains present in the emulsion layer meet the following conditions (1), (2) and (2). 4. A four-tone photosensitive source material for negatives, characterized in that the X-ray diffraction pattern of the emulsion (according to the method described in the text) yields two distinct peaks.

■ The outermost layer (shell S) has a silver iodide content of 6 mol or more, and ■ The innermost layer has a silver iodide content of J
Twin grains with mo1% or more less phase (core S) and aspect ratio of g or less;
It is 0m01% or less.

3. In the above 1, the peak diffraction intensity of the layer with a high silver iodide content is 172o-i7/ that of the layer with a low silver iodide content.

Hiroshi: The light-sensitive material of item 1 above, wherein the relative standard deviation of the distribution of the inter-grain normal content of total/% silver halide grains in the emulsion is 370% or less.

[Brief explanation of the drawing]

FIG. 1 shows the X-ray diffraction patterns of emulsion λ and emulsion j in Example-7. The vertical axis is the diffraction intensity. The horizontal axis shows the silver iodide content. Patent Applicant: Fuji Photo Film Co., Ltd. Figure 1, Figure 2 (Iotsu Ministry, Aikura 2M Children (71%) Procedural Amendment 1, Indication of Case: Showa Otsu 3rd Patent Application No. 1/jtf-
/ No. 2, Name of the invention: Silver halogenated photographic light-sensitive material for negatives 3, Relationship with the case of the person making the amendment: Patent applicant: Address: 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Name: (520) Fuji Photo Film Co., Ltd. 4: Subject of amendment The "Detailed Description of the Invention" column of the specification & Contents of the amendment The grant money in the "Detailed Description of the Invention" section of the specification shall be amended as follows. 2) From "When core particles are formed" on the jth line of the isth page to the 1st page! Delete everything up to the line "Preferable." 3) No. J! After “soda thiosulfate” on page j line, is “and triethylthiourea”? insert. 4) On page 62/line j, after “/lLt,lj” is “wodimethylselenourea”? insert. Procedural amendment

Claims (2)

[Claims] (1) In a photographic light-sensitive material having at least one silver halide emulsion layer on a support, chemically sensitized silver halide grains contained in one emulsion in the emulsion layer are [1] the outermost layer. (shell part) silver iodide content is 6 mol%
[2] The innermost layer has a silver iodide content of 3 m from the outermost layer.
[3] A silver halide negative characterized by being twin grains having an aspect ratio of 8 or less that allows the phases [1] and [2] to be clearly distinguished Photographic material for (2) The silver halide photographic material according to claim 1, wherein the silver iodide content of the entire grain is 10 mol% or less.