JPH04208936A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide photographic sensitive material having high sensitivity and contrast by using silver halide particles contg. a metallic complex having at least two cyan ligands represented by a specified formula. CONSTITUTION:This silver halide photographic sensitive material has a silver halide emulsion layer contg. about 0.01-40 mol% surface latent image type silver halide particles each having a core made practically of silver bromide or silver iodobromide, a first coating layer made practically of silver iodobromide at the outside of the core and a second coating layer at the outside of the first layer. The silver iodide content of the first layer is higher than that of the core by about >=10mol% and the silver halide particles contain a metallic complex having at least two cyan ligands represented by formula I or II. In the formulae I, II, M1 is Fe, Re, Os, Ir or Pt, M2 is Pt or Au, L is a ligand other than CN, a is 0, 1 or 2, b is 0, 1 or 2, n is -2, -3 or -4 and m is -1 or -2.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a silver halide photographic light-sensitive material, and more specifically, a silver halide photographic material with high sensitivity and high contrast.

This invention relates to a silver halide photographic material that has excellent pressure resistance, which is a problem in practical use.

(Prior Art) One of the basic properties required of a photographic silver halide emulsion is high sensitivity, low fog, and fine grain.

As a way to increase the sensitivity of an emulsion, ω it was possible to increase the number of photons absorbed by a single particle, and ■ increase the efficiency with which photoelectrons generated by absorption of photons are converted into silver clusters (latent images) (3). In order to effectively utilize the latent image, it is possible to increase the development activity. However, when the particle size is increased, the number of photons absorbed by each particle increases, but the grain size becomes coarser. Increasing development activity is effective in increasing sensitivity, but
Often accompanied by increased fogging. In order to increase the sensitivity of an emulsion without deteriorating grain and increasing fog, it is most preferable to increase the efficiency with which photoelectrons are converted into latent images, ie, to increase quantum sensitivity.

In order to increase the quantum sensitivity, it has been done in the past to add a group Ⅰ metal compound having a cyanigant during the formation of silver halide grains. For example, special public show 4g-3537
3 contains 10− per mole of silver during silver halide grain formation.
It is stated that when 7 to 1 O-3 mol of a water-soluble iron compound is present, a high-contrast emulsion can be obtained without impairing sensitivity. In addition, in Japanese Patent Publication No. 49-14265, the particle size is 0.
9. 1 per mole of silver in the following silver halide grains:
It is reported that an emulsion in which 0-s to 10-3 mol of a group Ⅰ metal compound is added during grain formation and is further spectrally sensitized with a merocyanine dye has high sensitivity at high illuminance. However, although high sensitivity can certainly be obtained by following these techniques,
At the same time, the internal sensitivity increased, so the degree of increased sensitivity was small. Furthermore, in JP-A-1-121844, in a photosensitive silver halide grain in which one grain is composed of two or more different halogen compositions, silver halide 1 in that part is
It is disclosed that an emulsion containing 10-' mole or more of divalent iron ions per mole has high sensitivity. However, it is important to note that the effect of this technique appears only when divalent iron ions are contained, and there is no particular suggestion regarding the species of the ligand. Moreover, JP-A-2-20854 discloses R e having at least four cyanigants.

It is disclosed that doping silver iodobromide with a hexacoordination complex of Ru, O5, or Ir increases the sensitivity and fog stability during emulsion storage, and further reduces low-light reciprocity law failure. has been done. However, although this technique can certainly increase stability, it also has the drawback of significantly increasing internal sensitivity and decreasing sensitivity. More importantly, this patent has no suggestion or description of the Fe compound with the most effective cyanigant.

As a photographic silver halide emulsion for practical use, it is preferable that the emulsion has a high contrast. For example, in the case of negative color film for photography, if a light-sensitive material with the same gradation is produced using an emulsion with higher contrast, the amount of coated silver can be reduced. Furthermore, if a high-contrast emulsion is used in the high-sensitivity layer of a multilayer photographic color reversal film, it is possible to improve the gradation and the graininess of highlight areas more preferably. Emulsions with high contrast are also preferred in sensitive materials for graphic arts.

On the other hand, various mechanical stresses are applied to sensitive materials coated with silver halide emulsions for practical use. For example, general photographic negative film is wound into a cartridge, folded when loaded into a camera, and pulled for frame advance. Therefore, if fogging or a change in sensitivity occurs due to pressure, it becomes a serious problem in practice.6 In particular, sensitive materials with high sensitivity tend to have a large change in sensitivity due to pressure, which has been a problem. For this reason, for photographic silver halide emulsions, it is a practically important performance to have little fog and change in sensitivity due to pressure.

JP-A No. 60-35726 discloses an inner core made of silver bromide or silver iodobromide, a first coating layer made of silver iodobromide on the outside of the inner core, and an odor coating layer on the outside of the first coating layer. a second coating layer made of silver oxide or silver iodobromide, the ratio of the projected area diameter to the thickness of the grains is less than 5, is more than 10 mol % higher than the iodine content of the internal core, and ■ the silver halide content in the first coating layer is 0.01 to 30 mol % of the total grain, and the pressure characteristics are It is shown that it is good. Although it is true that fogging or sensitization in stressed areas can be significantly improved by following this technique, improvement in desensitization in stressed areas is particularly important for highly sensitive emulsions. It wasn't enough.

German Patent No. 2230214 also discloses that silver halide emulsions formed in the presence of alkali ferricyanides or alkaline ferrocyanides can reduce pressure fog.

(Problems to be Solved by the Invention) An object of the present invention is to provide a silver halide photosensitive material with high sensitivity and high contrast. Furthermore, it is an object of the present invention to provide a silver halide photosensitive material which simultaneously improves the pressure characteristics of the above-mentioned silver halide photosensitive material, that is, sensitivity increase/decrease due to pressure, and pressure blur.

(Means for Solving Problem W) The objects of the present invention can be achieved using the following silver halide photosensitive material.

1) In a silver halide photographic material having at least one light-sensitive silver halide emulsion layer on a support, the silver halide layer consists essentially of silver bromide or silver iodobromide. an inner core, a first coating layer provided outside the inner core consisting essentially of silver iodobromide, and further provided outside the first coating layer substantially consisting of silver bromide or silver iodobromide; The silver iodide content of the first coating layer is about 10 mol% or more higher than the silver iodide content of the inner core, and The ratio of silver halide in the first coating layer to the whole is about 0.01 to 40 mol %, and the grains have at least two cyanigants, and the following general formula (C-1) or [C A silver halide photographic material comprising a metal complex represented by -2].

[M□(CN)e-aLako (C-
I, ][Mz (CN)4-b L bE
(CII) (wherein, Mx: Fe, Ru, Re, ○s, Ir or ptMz:Pt or Au L:CN other than a: Q, 1 or 2 b: Q, 1 or 2 n 2. -3 or -4 mne 1 or -2) 2) The silver halide photographic light-sensitive material described in 1) above, containing surface latent image type silver halide grains containing an Fe compound having at least 4 cyanigants.

The size of the silver halide grains of the present invention is expressed by the projected area diameter, where the projected area diameter refers to the diameter of a circle having an area equal to the projected area of the grain.

The size of the silver halide grains of the present invention is 0.5 to 5.
．． 0μ is preferable, and 1.0 to 3.0μ is more preferable.

When the inner core of the present invention is made of silver iodobromide, it is preferably a homogeneous solid solution phase. Homogeneous here means that in the distribution of silver iodide content, the silver iodide content of 95 mol% of silver halide in the inner core falls within the range of ±40% of the average silver iodide content. means.

Regarding the halogen composition of the internal core, the average content of iodine is preferably 10 mol% or less, more preferably 0 to 10% by mole.
It is 5 mol%, particularly preferably 0 to 3 mol%.

The proportion of silver in the inner core relative to the total silver in one particle is preferably 5 mol % or more, more preferably 10 to 95 mol %.

The silver iodide content of the first coating layer is 10 mol% or more higher than the silver iodide content of the inner core, preferably 20 mol% or more, particularly preferably 40 mol% or more.

Further, the silver iodide content of the first coating layer is 10 mol% to
100 mol%, preferably 20 mol% to 100 mol%
It is mol%, more preferably 40 mol% to 100 mol%.

The proportion of silver in the first coating layer relative to the total silver of the particles is 0.01 to 40 mol%, preferably 0.01 to 30 mol%, more preferably 0.01 to 10 mol%, particularly preferably It is 0.02 to 0.5 mol%.

When the second coating layer consists of silver iodobromide, it does not necessarily have to be homogeneous, but it is more preferably a homogeneous silver iodobromide.

Further, the second coating layer needs to sufficiently cover the first coating layer, and for this purpose, the average thickness of the second coating layer is preferably 0.02μ or more, more preferably 0.04μ.
That's all.

The silver iodide content of the second coating layer is preferably 0 to 10 mol%, more preferably 0 to 5 mol%, particularly preferably 0 to 10 mol%.
It is 3 mol%.

Further, the silver iodide content of the second coating layer is preferably lower than that of the first coating layer.

The proportion of silver in the second coating layer relative to the total silver of the particles is preferably 5 to 90 mol%.

The internal structure of the silver halide grains of the present invention can be measured by methods well known to those skilled in the art. That is, the test particles sliced in advance with a microtome were
By mapping the silver iodide content within the grain by scanning with an analytical electron microscope using an electron beam with a spot of The proportion occupied by silver and the silver iodide content of each part can be measured. Here, the boundary between each portion can be determined as the point of maximum change in silver iodide content. It should be noted that these measured values match the prescribed values when each portion is formed by the so-called double jet method.

Although the size distribution of the silver halide grains of the present invention is arbitrary, it is more desirable that they be monodisperse. Here, monodisperse means a dispersion system in which 95% of the particles have a size within ±60%, preferably within ±40% of the number average particle diameter. Here, the number average particle diameter is the number average diameter of the projected area diameter of particles.

The proportion of silver halide grains contained in the emulsion layer containing silver halide grains of the present invention may be arbitrarily selected, but is preferably 40% or more in terms of silver amount based on all silver halide grains. Particularly preferably, it is 90% or more.

Fe, Ru, Re, ○s, Ir, Pt or A having at least two cyanigants used in the present invention
The metal complex u is preferably represented by the following general formula [C-1) or (c-■).

[Ml (CN)s-a La]” (CI
) [M2 (CN)4-b Lbko” (C-11
) In the formula, M: Fe, Ru, Re, Os, Ir or ptM2: Ligand other than Pt or Au L:CN a: o, 1 or 2 b: o, 1 or 2 n 2. -3 or -4 mney 1 or -2 Among these, the metal complex represented by the general formula (C-1) is more preferably used. Further, the general formula % formula % or Ir is preferable, and among them, Fe is the most preferable.

Specific examples of metal complexes having at least two cyanigants used in the present invention are shown in Table A below. As counter ions for these metal complexes, ammonium and alkali metal ions such as sodium and potassium are preferably used.

The content of the metal complex having at least two cyanigants used in the present invention is 10% per mole of silver halide.
It is preferably -7 mol or more and 10-3 mol or less, and more preferably 1, OX 10-' mol or more and 5X10-' mol or less per mole of silver halide.

The metal complex having at least two cyanigants used in the present invention may be added and contained at any stage before or after the preparation of silver halide grains, that is, nucleation, growth, physical ripening, and chemical sensitization. Furthermore, the metal complex having at least two cyanigants contained in the silver halide grains may be added in several portions and may be added in several portions. A layer not containing a metal complex may be provided further outside the second coating layer containing the metal complex described here, which is preferably contained in the second coating layer.

These metal complexes can be dissolved in water or a suitable solvent and added directly to the reaction solution during the formation of silver halide grains, or in an aqueous halide solution or silver salt aqueous solution for forming silver halide grains. Alternatively, it is preferable to incorporate it by adding it to other solutions to form particles.

It is also preferable to incorporate these metal complexes by adding and dissolving silver halide fine particles containing metal complexes in advance and depositing them on other silver halide particles.

The hydrogen ion concentration in the reaction solution when these metal complexes are added is preferably PH=1 or more and 1O or less, and more preferably PH=3 or more and 7 or less.

In addition to the metal complex having at least two cyanigants, the silver halide grains of the present invention preferably contain the following metal complexes or metal salts.

hexachloroiridium (m) or (IV) salt, hexamine iridium (DI) or (IV) salt, trioxalatoiridium (IF) or (IV) salt,
Ferric hexacyano(II) or (m) salt, ferric thiocyanate or ferric thiocyanate.

The amount of iridium ion added is preferably in the range of 10-9 mol to 10-G mol per mol of silver halide, and 10-' mol to 10-' mol per mol of silver halide.
Most preferred are molar ranges. The amount of iron ion added is preferably in the range of 10-8 to 10-4 mol per mol of silver halide, and 10-4 mol per mol of silver halide.
Most preferred is a range of 7 to 10-4 moles.

Next, a method for producing the silver halide emulsion of the present invention will be described. That is, generally, after forming a core (inner core) consisting of silver bromide or silver iodobromide (iodine content of 10 mol% or less), silver iodobromide is added onto the core by a halogen substitution method or a coating method. Alternatively, a first coating layer made of silver iodide is formed, and a second coating layer made of silver iodobromide or silver bromide having a different halogen composition from the first coating layer is provided on the first coating layer. In the method for producing layered silver halide grains, the iodine content of the first coating layer is 10 mol % or more higher than that of the inner core, and the amount of silver in the first coating layer is 0.0% of the total silver halide grain. 01 to 40 mol%.

Details are described below.

First, the inner core of the silver halide grains of the present invention is P.

Chimie et Phys by G 1afkides
igue Photography (Paul
Monte 1, 1967), G, F.

Written by Duffin Photographic E mu
lsion Chemistry (The Foc
al Press, 1966), V.L.

Making an by Zelikman et al.
dCoating Ph.

Tographic E mulsion (The
Focal Press, 1964). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt and soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. . It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).

As one type of simultaneous mixing method, a method in which PAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondrald double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Two or more types of silver halide emulsions formed separately may be mixed and used.

When preparing the inner core of silver halide grains, it is preferable that the inner core has a uniform halogen composition. When the inner core is silver iodobromide, it is preferable to use the double jet method or the Chondrald double jet method. Furthermore, when the inner core is silver bromide, the one-sided mixing method is preferred.

The PAg used when preparing the inner core varies depending on the reaction temperature and the type of silver halide solvent.

Preferably it is 7-11. Further, it is preferable to use a silver halide solvent because the grain formation time can be shortened.

For example, commonly known silver halide solvents such as ammonia and thioether can be used.

The shape of the internal core may be plate-like, spherical, or twin-crystalline. An octahedron, a cube, a tetradecahedron or a mixed system can be used.

Further, the size distribution of the inner core may be polydisperse or monodisperse, but monodisperse is more preferable.

Here, "monodisperse" has the same meaning as described above.

Also, to make the particle size uniform, British patent 1.53
No. 5,016, Special Publication No. 48-36890, No. 52-16
364, etc., there is a method of changing the addition rate of silver nitrate or aqueous alkali halide solution depending on the grain growth rate, and there is a method described in U.S. Pat. It is preferable to use a method of changing the concentration of the aqueous solution as described above to grow quickly within a range that does not exceed the critical supersaturation degree.

These methods do not cause re-nucleation and each silver halide grain is coated uniformly, and therefore are preferably used when introducing the first and second coating layers described below.

The first coating layer of the silver halide grains of the present invention can be provided by a conventional halogen substitution method, a silver halide coating method, or the like after subjecting the formed inner core to a desalting step, if necessary.

The halogen substitution method can be carried out, for example, by adding an aqueous solution consisting mainly of an iodo compound (preferably potassium iodo), preferably at a concentration of 10% or less, after the internal core is formed. At this time, the number of moles of silver in the entire finished particle is 0.01
-30 mole % of iodo compound is added. Further, at this time, PAg is preferably 5 to 12. For details, see U.S. Pat.
, 020, JP-A-55-127549, and the like. At this time, in order to reduce the difference in iodine distribution between particles in the first coating layer, it is desirable to add the iodine compound aqueous solution over 10 minutes or more at a concentration of 10 -2 mol % or less.

Further, as a method for newly coating the inner core with silver halide, it can be carried out, for example, by simultaneously adding an aqueous halide solution and an aqueous silver nitrate solution, that is, by a simultaneous mixing method or a Chondrald double jet method.

For details, see Japanese Patent Application Laid-open No. 53-22408, Japanese Patent Publication No. 43
Publication No.-13162, J.

This can be carried out by the method described in Photo, Sci, 24.198 (1976).

At this time, 0 for the number of moles of silver in the entire completed particle.
．． 01 to 30 mol % of silver nitrate, an iodine compound of equal mole or more (up to about twice the amount), and, if necessary, an aqueous halide solution containing silver bromide are added.

The PAg to be used when forming the first coating layer varies depending on the reaction temperature and the type and amount of silver halide solvent, but preferably those mentioned above are similarly used.

As a method for forming the first coating layer, a simultaneous mixing method or a Chondral double jet method is more preferable.

The second coating layer of the silver halide grains of the present invention further includes a silver halide having a halogen composition different from that of the first coating layer on the outside of the inner core having the first coating layer on the surface. It can be provided by a coating method such as a mixing method or a Chondrald double jet method.

Regarding these methods, the method of providing the first coating layer described above is similarly used.

When introducing the second coating layer, since the halogen composition of the second coating layer is different from the halogen composition of the first coating layer,
Since the second coating layer may be difficult to precipitate on the surface of the first coating layer, it is necessary to consider changes in the degree of critical supersaturation. Further, it is preferable to increase the number of moles added per unit time as the total surface area of one particle increases.

When the second coating layer is silver bromide, a method (one-sided mixing method) in which an aqueous silver nitrate solution is added in the presence of an inner core having bromide and the first coating layer in advance can also be used.

The halogen composition of the second coating layer is preferably uniform, but for this purpose, when the second coating layer is made of silver iodobromide, it is formed by a simultaneous mixing method or a Chondrold double jet method. is preferable. Further, when the second coating layer is silver bromide, it is preferable to use a one-sided mixing method.

Regarding the iodine content of the first coating layer of the silver halide grains of the present invention, for example, J, 1. Goldstein (G
oldstein), D.B.
iams) r X-ray Analysis in TEM/ATEM,” Scanning Electron Microscopy (1977), Volume 1 (IIT Research Institute), Page 651 (March 1977). It can also be determined by the method described.

In preparing the silver halide grains of the present invention, soluble salts are removed from the emulsion after precipitation of the second coating layer or after physical ripening, or if necessary, from the emulsion after internal nucleation or after formation of the first coating layer. To achieve this, a Zudel water washing method in which gelatin is gelatinized may be used, and inorganic salts, anionic surfactants, anionic polymers (e.g. polystyrene sulfonic acid), or gelatin derivatives (e.g. acylated gelatin, carbamoyl A sedimentation method (flocculation) using gelatin (gelatin) may also be used.

Silver halide emulsions are usually chemically sensitized on the grain surfaces. For chemical sensitization, e.g. HoF rieser
Edited by Die Grundlagen der Photo
graphischen process with S
ilberhalogeniden (Acades+
1sche Verlagsgesellschaft
, 1968) 675~? The method described on page 34 can be used.

That is, a sulfur sensitization method using a compound containing sulfur that can react with silver ions or active gelatin, a reduction sensitization method using a reducing substance, a noble metal sensitization method using gold or other noble metal compounds, etc. are used alone or in combination. be able to. As the sulfur sensitizer, thiosulfates, thioureas, thiazoles, rhodanines, and other compounds can be used, and specific examples thereof are described in U.S. Pat. No. 1,574,944.
No., No. 2,410,689, No. 2,410,689, 2
, No. 278,947, No. 2,728,668, 3.65
No. 6,955, No. 4,032,928, No. 4,067.7
It is described in No. 40. As the reduction sensitizer, for example, stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, and silane compounds can be used,
Specific examples thereof include U.S. Pat.
, No. 609, No. 2,983,610, No. 2,694,63
No. 7, No. 3,930,867, and No. 4,054,458. For noble metal sensitization, in addition to total complex salts,
Complex salts of metals in group I of the periodic table, such as platinum, iridium, and palladium, can be used, and specific examples thereof include U.S. Pat.
No. 399,083, No. 2,448,060, British Patent 6
No. 18,061, etc.

The complex salt particles of the present invention can be produced using a combination of two or more of these chemical sensitization methods.

The amount of coated silver is arbitrary, but is preferably 1000 to 15000 μ/M, more preferably 20
00■/I or more and 10000■/Bo or less.

Additionally, photosensitive layers containing the particles may be present on both sides of the support.

Gelatin is advantageously used as the binder or protective colloid in the photographic emulsion of the invention, but other hydrophilic colloids can also be used.6 Such hydrophilic colloids include proteins, such as gelatin derivatives. , graft polymers of gelatin and other polymers, albumin,
Casein; cellulose derivatives, such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates; acid derivatives, such as sodium alginate,
Starch derivatives; synthetic hydrophilic polymer substances, such as single or copolymers of polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, and polyvinylpyrazole. Can be used.

In addition to lime-processed gelatin, acid-processed gelatin and Buel, Sac, Sci, Phot, J.
apan, N.

16.30 (1966) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used. As gelatin derivatives, various compounds such as acid halides, acid anhydrides, incyanates, bromoacetic acids, alkanesultones, vinylsulfonamides, maleimide compounds, polyalkylene oxides, and epoxy compounds are added to gelatin. The product obtained by the reaction is used.

The photographic emulsion of the present invention can contain various compounds for the purpose of preventing fogging or stabilizing photographic performance during the manufacturing process, storage, or photographic processing of the light-sensitive material. i.e. compounds known as antifoggants or stabilizers, such as azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles. mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-
5-mercaptotetrazoles): mercaptopyrimidines; mercaptotriazines; thioketo compounds, such as oxazolinthione; azaindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxy substituted (1,3,3a,7) tetra azaindenes), pentaazaindenes; benzenethiosulfonic acid, benzenesulfinic acid, and benzenesulfonic acid amide.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material of the present invention is used as a coating aid, antistatic, improves slipperiness, emulsification and dispersion,
Various surfactants may be included for various purposes such as preventing adhesion and improving photographic properties (for example, accelerating development, increasing contrast, and sensitizing).

Examples of such surfactants include non-ionic surfactants such as saponins (steroids), alkylene oxide derivatives such as polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkyl amines or amides, silicone polyethylene oxide adducts), glycidol derivatives (e.g. alkenyl succinic acid polyglycerides, alkylphenol polyglycerides), polyhydric Fatty acid esters of alcohols, alkyl esters of sugars Anionic surfactants containing tetrafunctional groups such as carboxyl groups, sulfo groups, phospho groups, sulfate ester groups, and phosphoric ester groups 2 For example, alkyl carboxylates, alkyl sulfonates , anikylbenzene sulfonate, alkylnaphthalene sulfonate, alkyl sulfate, alkyl phosphate ester, N-acyl-N-alkyl taurine, sulfosuccinate, sulfoalkyl polyoxyethylene alkylphenyl ether , polyoxyethylene alkyl phosphates; amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphates, alkyl betaines, amine oxides; cationic surfactants such as alkyl amine salts, Aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used.

The photographic emulsion in the present invention may be spectrally sensitized with methine dyes and others. These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits supersensitization.

Useful sensitizing dyes, supersensitizing dye combinations, and supersensitizing substances are available from Research Disclosure (Res.
176, 17
643 (published December 1978), page 23, item 5 of ■.

The photographic material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer.

For example chromium salts (e.g. chromium alum, chromium acetate)
, aldehydes (e.g. formaldehyde, glyoxal, geltaraldehyde), N-methylol compounds (e.g. dimethylol urea, methylol dimethylhydantoin), dioxane derivatives (e.g. 2,3-dihydroxydioxane), activated vinyl compounds (e.g. ,
1,3.5-Triacryloyl-hekihydro-5-)-
riazine, 1,3-vinylsulfonyl-2-propanol), active halogen compounds such as (2,4-dichloro-
(6-hydroxy-8-triazine), mucohalogen acids such as (mucochloric acid, mucophenoxychloric acid) can be used alone or in combination.

The photographic light-sensitive material of the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer in the photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability. For example, alkyl (meth)acrylates, alkoxyalkyl (meth)acrylates, glycidyl (meth)acrylates, (meth)acrylamides, vinyl esters (e.g. vinyl acetate), acrylonitrile, olefins, styrene alone or in combination, or together with acrylic acid, methacrylates, etc. A polymer containing a combination of acrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth)acrylate, sulfoalkyl (meth)acrylate, and styrene sulfonic acid as a monomer component can be used.

The photographic emulsion layer of the photographic light-sensitive material of the present invention contains a color-forming coupler, that is, a color-forming coupler that can form a color by oxidative coupling with an aromatic primary amine developer (for example, a phenylenediamine derivative or an aminophenol derivative) in a color development process. It may also contain compounds. For example, magenta couplers include 5-pyrazolone couplers, pyrazolobenzimidazole couplers, cyanoacetylcoumarone couplers,
There are open-chain acylacetonitrile couplers, yellow couplers include acylacetamide couplers (eg, benzoylacetanilides, pivaloylacetanilides), and cyan couplers include naphthol couplers and phenol couplers. These couplers are preferably non-diffusive and have a hydrophobic group called a ballast group in the molecule. The coupler may be either 4-equivalent or 2-equivalent to silver ion. It may also be a colored coupler that has a color correction effect or a coupler that releases a development inhibitor during development (so-called DIR coupler). In addition to DIR couplers,
The products of the coupling reaction may be colorless and include colorless DIR coupling compounds that release development inhibitors.

In carrying out the present invention, the following known antifading agents may be used in combination, and the color image stabilizers used in the present invention may be used alone or in combination of two or more. Known antifading agents include hydroquinone derivatives, gallic acid derivatives, p-alkoxyphenols, p-oxyphenol derivatives, and bisphenols. - The photosensitive material of the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, benzotriazole compounds substituted with aryl groups, 4-thiazolidone compounds, benzophenone compounds, cinnamic acid ester compounds, butadiene compounds, benzoxazole compounds, and ultraviolet absorbing polymers can be used. These ultraviolet absorbers may be fixed in the hydrophilic colloid layer.

The photosensitive material of the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes.

Among them, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful.

The photosensitive material of the present invention uses hydroquinone derivatives, aminophenol derivatives, gallic acid derivatives,
It may also contain ascorbic acid derivatives.

The invention is also applicable to multilayer, multicolor photographic materials comprising on a support at least two layers with different spectral sensitivities.

Multilayer natural color photographic materials usually have a red-sensitive emulsion layer on a support,
It has at least one green-sensitive emulsion layer and at least one blue-sensitive emulsion layer. The order of these layers can be arbitrarily selected as required. Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case.

In the photographic material of the present invention, the photographic emulsion layer and other hydrophilic colloid layers can be coated on the support or on other layers by various known coating methods. For coating, a tip coating method, a roller coating method, a curtain coating method, an extrusion coating method, etc. can be used. U.S. Patent 2,681,294
The method described in Japanese Patent No. 2,761,791 and Japanese Patent No. 3,526,528 is an advantageous method.

The support is preferably a cellulose ester film such as cellulose triacetate film, a polyester film such as polyethylene terephthalate film, or paper coated with an α-olefin polymer.

The photosensitive materials to which the present invention is applied include, for example, color negative films, color reversal films (inner and outer molds), color papers, color positive films, color reversal papers,
Any of color photographic materials such as color diffusion transfer process and die transfer process, and black and white photographic materials such as black and white negative film and lithographic film may be used. Among them, color negative film, color reversal film (inner and outer mold), color paper, color positive film,
More favorable results can be obtained when the present invention is applied to color reversal paper, but it is most preferably applied to color reversal films and color reversal papers. Research Disclosure'r (Resea
rch Disclosure) 176 No. 28-3
Any of the known methods and known treatment liquids as described on page 0 (RD-17643) can be applied. This photographic processing may be either photographic processing that forms a silver image (black and white photographic processing) or photographic processing that forms a dye image (color photographic processing), depending on the purpose. The processing temperature is usually selected between 18°C and 50°C, but temperatures below 18°C or above 50°C may also be used.

The developer used in black-and-white photographic processing can contain known developing agents. As the developing agent, dihydroxybenzenes (e.g. hydroquinone), 3-pyrazolidones (e.g. 1-phenyl-3-pyrazolidone), aminophenols (e.g. N-methyl-P-aminophenol), etc. may be used alone or in combination. I can do it.

The developer generally contains a known preservative, alkaline agent, pH
It contains a buffering agent, an anti-fogging agent, etc., and may further contain a solubilizing agent, a toning agent, a development accelerator, a surfactant, an antifoaming agent, a water softener, a hardening agent, a viscosity imparting agent, etc., if necessary.

As the fixer, one having a commonly used composition can be used.

As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as fixing agents can be used.

The fixer may contain a water-soluble aluminum salt as a hardener.

When forming a dye image, conventional methods can be applied.

For example, negative-positive method (for example, "Journal of
theSociety of Motion Pic
ture and Television Engine
61 (1953), pp. 667-701): develop with a developer containing a black and white developing agent to produce a negative silver image, followed by at least one -like exposure or other A color reversal method in which a dye-positive image is obtained by performing appropriate fogging treatment and subsequent color development.A photographic emulsion layer containing two dyes is exposed and developed to create a silver image, and this is used as a bleaching catalyst to bleach the dyes. A silver dye bleaching method is used.

Color developers generally consist of an alkaline aqueous solution containing a color developing agent. The color developing agent is a known general aromatic amine developer, such as phenylene diamines (e.g. 4-amino, N-N, N-diethylaniline, 3-methyl-4-
Amino-N, N-diethylaniline, 4-amino-N-
Ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N
-β-methanesulfamide ethylaniline, 4-amino-3-methyl-N-ethyl-N-β-methoxyethylaniline) can be used.

In addition, L +F, A, Mason's photo
graphicProcessing Che+m1s
2 of try (Focal Press, 1966)
pp. 26-229, U.S. Patent No. 2,193,015, 2
, No. 592.364, JP-A-48-64933, etc. may be used.

The color developer may also contain other additives such as a PH buffer, a development inhibitor, or an antifoggant. Also, if necessary,
It may also contain water softeners, preservatives, organic solvents, development accelerators, dye-forming couplers, competitive couplers, fogging agents, auxiliary developers, viscosity-imparting agents, polycarboxylic acid chelating agents, antioxidants, and the like.

After color development, the photographic emulsion layer is usually bleached. The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. As the bleaching agent, for example, compounds of polyvalent metals such as iron (m), cobalt (IV), chromium (VI), and copper (■), peracids, quinones, and nitroso compounds are used.

For bleach or bleach-fix solutions, see U.S. Patent No. 3,042,52.
No. 0, No. 3,241,966, Special Publication No. 45-8506
Bleaching accelerators described in Japanese Patent Publication No. 45-8836, etc.
In addition to the thiol compound described in JP-A-53-65732, various additives can also be added.

The present invention is most preferably used in color reversal photosensitive materials, and the processing solution and processing steps for color reversal photosensitive materials will be described below.

Among the processing steps, the steps from black and white development to color development are as follows.

1) Black and white development - water washing, reversal, one color development 2) Black and white development - water washing, light reversal, one color development 3) Black and white development -
The water washing steps 1) to 3) are all performed in U.S. Patent Nos. 4 and 8.
By replacing the rinsing step described in No. 04,616, it is possible to simplify the process and reduce waste liquid.

Next, the steps after color development will be explained.

4) Color development - Adjustment - Bleach - Constant wear - Wash with water - Stable 5) Color development - Wash with water - Bleach - Constant wear - Wash with water - Stable 6) Color development - Adjustment - Bleach - Wash with water - Constant wear - Wash with water - Stable 7) Color development - Wash with water - Bleaching - Washing with water - Stable - Washing with water - Stable 8) Color development - Bleach - Fixed with water - Stable 9) Color development -
Bleach - Bleach-fixing - Washing - Stable 10) Color development - Bleach - Bleach fixing - Constant fixing - Washing - Stable 11) Color development - Bleach - Washing - Constant fixing - Washing - Stable 12)
Color development - Adjustment - Bleach fixing - Washing - Stable 13) Color development - Washing - Bleach fixing - Washing - Stable 14) Color development - Bleach fixing - Washing - Stable 15) Color development - Constant fixing - Bleach fixing - Washing - Stable 4) In the treatment steps 15) to 15), the water washing step immediately before the stabilization step may be removed, or conversely, the final stabilization step may not be performed. Above steps 1) to 3
) Any one of the steps 4) to 15) are connected to form a color reversal step.

A known developing agent can be used in the black and white developer used in the present invention. Examples of developing agents include dihydroxybenzenes (e.g. hydroquinone), 3-pyrazolidones (e.g. 1-phenyl-3-pyrazolidone)
, aminophenols (e.g. N-methyl-P-aminophenol), 1-phenyl-3-pyrazolines, ascorbic acid and 1,2°3,4-tetrahydroquinoline as described in U.S. Pat. No. 4,067.872. A heterocyclic compound in which a ring and an intrene ring are condensed can be used alone or in combination.

The black and white developer used in the present invention may contain, if necessary, preservatives (e.g. sulfites, bisulfites), buffers (e.g. carbonates, boric acid, borates, alkanolamines), alkaline agents (e.g. hydroxides, carbonates), solubilizing agents (e.g. polyethylene glycols and their esters), PH regulators (e.g. organic acids such as acetic acid), water softeners (e.g. aminopolycarboxylic acids, organic phosphonic acids) , phosphonocarboxylic acids), sensitizers (e.g., quaternary ammonium salts), antifoggants (e.g., potassium bromide, benzotriazole, 1-phenyl-5-mercaptotetrazole), development accelerators (e.g., organic thioether compounds) ), a surfactant, an antifoaming agent, a hardening agent, and a viscosity imparting agent.

The black and white developer used in the present invention must contain a compound that acts as a silver halide solvent, and the sulfite added as a preservative as described above usually plays this role. The sulfite and other usable silver halide solvents include, for example, KSCN, Na5CN, 2S
03, Na25o,, K2S2O5, Na, 520S,
2S20. , N a , S 20.

The pH value of the developer thus adjusted is selected to be sufficient to provide the desired density and contrast, and is in the range of about 8.5 to about 11.5.

The reversal bath used after black and white development can contain a known fogging agent. Examples of fogging agents include stannous ion complex salts, such as stannous ion-organophosphate complex salts (
U.S. Pat.
No. 16), stannous ion-aminopolycarboxylic acid complex salts (U.S. Pat. No. 1,209,050), boron compounds 1 such as boron hydride compounds (U.S. Pat. No. 2,
No. 984,567) and heterocyclic amine borane compounds (UK Patent No. 1,011,000). The pH of this fogging bath (reversal bath) ranges over a wide range from the acidic side to the alkaline side, and is in the range of 2 to 12, preferably 2.5 to 10, particularly preferably 3 to 9. In place of the reversal bath, a light reversal process by re-exposure may be performed, and the reversal step can also be omitted by adding the above-mentioned fogging agent to the color developing solution.

The color developing solution of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. As this color developing agent, aminophenol compounds are also useful, but p-phenylenediamine compounds are preferably used, and a representative example thereof is 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- Examples include 4-amino-N-ethyl-β-methoxyethylaniline and their sulfates, hydrochlorides, p-toluenesulfonates, and the like. Two or more of these compounds can be used in combination depending on the purpose.

The color developer may contain pH buffering agents such as alkali metal carbonates, borates or phosphates, bromide salts, iodide salts,
Development inhibitors or antifoggants such as benzimidazoles, benzothiazoles or mercapto compounds are generally included. In addition, if necessary, hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenylsemicarbazides, triethanolamine, catechol sulfonic acids, triethylenediamine (1,4-diazabicylo(2,2゜2)octane), etc. Various preservatives, organic solvents such as ethylene glycol and diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, and amines, dye-forming couplers, competitive couplers, and fogging agents such as sodium boron hydride. .

Auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting agents, various chelating agents such as aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids, such as ethylenediaminetetra Acetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-
Disulfonic acid, nitrilo-N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N.

N-tetramethylenephosphonic acid, ethylene glycol (
(0-hydroxyphenylacetic acid) and their salts are representative examples.

The pH of these color developing solutions and black and white developing solutions is generally 9 to 12. Although the amount of replenishment of these developing solutions depends on the color photographic light-sensitive material to be processed, it is generally 3Q or less per square meter of the light-sensitive material. When reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the area of contact with the air in the processing tank.

Furthermore, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

The color developer used in the present invention may contain a fluorescent whitening agent. As the fluorescent whitening agent, 4゜4'-diamino-2,2'-disulfostilbene-based compounds are preferred. .

The amount added is 0 to 5 g/Q, preferably 0.1 g to 4 g.
/ It is Q.

Furthermore, various surfactants such as alkylsulfonic acids, arylphosphonic acids, aliphatic carboxylic acids, and aromatic carboxylic acids may be added as necessary.

The processing temperature of the color developer of the present invention is 20 to 50°C, preferably 30 to 40°C. Processing time is 20 seconds to 5 minutes.
Preferably it is 30 seconds to 2 minutes. The amount of replenishment is preferably small, but is 100 to 1500-1, preferably 100 to 800 d per IM of the photosensitive material. More preferably 10
0d to 400-.

Further, the color developing bath may be divided into two or more baths as necessary, and the color developing replenisher may be replenished from the first bath or the last bath, thereby shortening the developing time and reducing the amount of replenishment.

The light-sensitive material of the present invention is subjected to desilvering treatment after color development. Desilvering treatment may be carried out immediately after color development without going through other processing steps, or it may be carried out immediately after color development to prevent unnecessary post-development and air fog, and to reduce the amount of color developer brought into the desilvering process. In addition, in order to wash out and detoxify the sensitive material parts such as sensitizing dyes and dyes contained in the photographic light-sensitive material and the color developing agent impregnated in the photographic light-sensitive material, after the color development processing, stopping, adjustment, and water washing are carried out. After passing through the following processing steps, a bleaching treatment or a bleach-fixing treatment may be performed.

The adjustment solution includes, for example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid,
1,3-propanediaminetetraacetic acid, cyclohexanediaminetetraacetic acid, sulfites such as sodium sulfite, ammonium sulfite, and various bleaching accelerators as described in the bleaching solution, such as thioglycerin, aminoethanethiol, sulfoethane. Thiols can be included. For the purpose of preventing scum, sorbitan esters of fatty acids substituted with ethylene oxide, such as those described in U.S. Pat. No. 4,839,262,
No. 059,446 and Research Disclosure 1
It is preferable to contain a polyoxyethylene compound described in Vol. 91, 19104 (1980).

After desilvering, the photosensitive material of the present invention is subjected to processing steps such as water washing and/or stabilization as described above. It is also possible to use a simple treatment method in which a stabilization treatment is performed without substantial washing with water after the treatment with fixing ability.

The rinsing water used in the rinsing step can contain known additives, if necessary. For example, water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid,
Bactericides and antifungal agents (for example, isothiazolones, organochlorine disinfectants, benzotriazole) that prevent the growth of various bacteria and algae, and surfactants that prevent dry load and unevenness can be used. or L, E,
West.

“Water Quality Criteria”
, Phot, Sci, andEng,, Vol.
9, No. 6, pages 343-359
(1965) and the like can also be used.

Further, the water washing step is preferably performed using a multi-stage countercurrent method, and the number of stages is preferably 2 to 4 stages. Two or more types of stabilizing solutions may be used in multiple stages. The amount of replenishment is 1 to 50 times, preferably 2 to 30 times, and more preferably 2 to 15 times the amount brought in from the previous bath per unit area.

The shorter the treatment time of the water washing step, the more effective the present invention will be.
In terms of rapid processing, the total processing time for washing and stabilization steps is 10
-50 seconds is preferable, and the effect is particularly remarkable in 10-30 seconds.

Further, the smaller the amount of replenishment in the water washing step, the greater the effect of the present invention, and it is preferably 50+++ffi to 400+aj2, particularly preferably 50 to 200 mQ, per 1M of photosensitive material.

As for the water used in the washing process, in addition to tap water, use water that has been deionized with an ion exchange resin to reduce the Ca and Mg concentration to 5■/Q or less, water that has been sterilized with halogen, ultraviolet germicidal lamps, etc. is preferable.

Further, the amount of waste liquid can be reduced by using a method in which the overflow liquid from the water washing step flows into a pre-bath having a fixing ability.

(Examples) Hereinafter, the present invention will be specifically explained by examples, but the present invention is not limited thereto.

Example 1 [1] Preparation of comparative samples 1-1-■ to O■ Preparation of silver iodobromide grains for A phase (inner core) 30 g of gelatin, 8 g of potassium bromide, and 42 cc of 25% aqueous ammonia solution were added to water IQ. Add an aqueous solution containing 250 g of silver nitrate per Ω (liquid A) into a container kept at 75°C while stirring.
800- and 780d of an aqueous solution (solution D) containing 5 g of potassium iodide and 206 g of potassium iodide per IQ.
They were simultaneously added by a double jet method while maintaining Br at 1.41. The silver halide grains thus obtained have a size defined by the projected area diameter (hereinafter the same) of 0.98-
These are octahedral silver iodobromide grains containing 2.1% of silver iodide.

■ Growth of phase C (coating layer) 34g of silver nitrate and 79g of water from the phase A emulsion described in ■
0 cc, gelatin tsg and 7.6 cc of acetic acid were mixed into a container kept at 75°C, while stirring.
4NAgNO, solution 650cc (solution C) and 1,
A solution of 650 cc of 09 N KBr solution mixed with 3.3 g of KI (liquid D) was simultaneously added by a double jet method while maintaining the pBr at 1.41. Note that the pH inside the container at this time was 6.1. The silver halide grains thus obtained are monodispersed octahedral grains with an average diameter of 1.42 μs, and have a uniform structure with a silver iodide content of 2 mol % in both the A phase and C phase.

The halogenated emulsion thus obtained was optimally sensitized with gold and sulfur using chloroauric acid and sodium thiosulfate.
After adding hydroxy-6-methyl-1,3゜3a,7-chitrazaindene and further adding a coating aid, the amount of silver was 4 g/rr? (Comparative sample I-l-■).

Next, K 4 [F e (CN ) s, to 3 [F
e(CN)s].

K, [Ru(CN)G], KJRe(CN)s
Ko, K4 [05(CN)-], K4 [I
r(CN)-ko, K2 [Pt(CN), ,].

Comparative Sample 1-1-■ Comparative samples 1-1-2 to 1-1-0 were prepared in exactly the same manner as above.

(Leaving space below) Table 1 In Table 1 above, the dope type refers to the chemical formula of the compound added to the D solution, and the amount added refers to the molar fraction of the compound added to the silver in the C phase. Indicates whether only

[2] Preparation of silver iodobromide in which the B phase (first coating layer) was introduced by the substitution method with iodide ions is the same as that of O from sample 1-1-■, but before moving on to the growth of the C phase. To 34 g of silver nitrate in the A phase emulsion, an aqueous solution containing 0.49 g of KI in 100 m12 was added over 10 minutes at 75°C to introduce the B phase, and then the silver iodide content was adjusted. A C phase (second coating layer) containing 2 mol % was provided to obtain 1.42-monodispersed octahedral particles. The samples thus obtained were designated as Samples 1-2-■ to O. However, the process conditions after chemical ripening are the same as in Example 1-[1].

[3] The preparation method of silver iodobromide with silver iodide B phase (first coating layer) introduced was the same as that for comparative samples l-1-■ to O, but
Before moving on to the growth of phase C, the amount of silver nitrate was 34 g (7
) To the A-phase emulsion, at 75°C, an aqueous solution containing 0.49 g of nitric acid in 100 mj2 and an equivalent amount of AgN0□ aqueous solution were simultaneously added over 10 minutes, and further Example 1-
[1] Phase C was grown in the same manner as in [1]. In this way, monodisperse octahedral halogen silver particles with a particle size of 1.42 tIM were obtained. However, the steps after chemical sensitization were the same, and the obtained coating samples were changed from 1-3-■ to O.

[4] Preparation of silver iodobromide with C phase (second coating layer) introduced at high pH The preparation method is the same as sample l-2-■, but after forming B phase by the substitution method with iodide ions. , when providing a C phase (second coating layer) with a silver iodide content of 2 mol%, 7.6 cc of acetic acid
Add 10 cc of 25% ammonia aqueous solution instead of 1.42. Monodisperse octahedral particles were obtained. The hydrogen ion concentration when forming the C phase was pH=10.2. A coated sample was prepared after chemical sensitization in the same manner as in Example 1-(1), and a comparative sample I-4- was bound.

Next, when forming C phase, K, [Fe(CN)
@] is lXl0−'mol1 for the number of moles of silver in the C phase
The above comparative sample l- except that it was added to give molar silver.
Comparative sample I-4-■ was prepared in the same manner as 4-■.

[5] Evaluation of sensitivity, gradation, and pressure characteristics of the above sample■
Sensitivity: A sample piece of sample 1-1-■ was wedge-exposed with an exposure time of 1/100 second and an exposure amount of 2 CMS, and was developed at 20° C. for 10 minutes using a processing solution having the following composition. After fixing, washing with water and drying, sensitometry was performed, and the reciprocal of the exposure amount giving an optical density of fog +0.1 was determined to be the sensitivity. Other samples were also subjected to the same treatment and sensitometry to determine their sensitivities. In fact, the sensitivities of the other samples were given as a ratio of the sensitivity of sample l-1-■ to the sensitivity of sample l-1-■, where the sensitivity of sample l-1-■ is 100, that is, as a relative sensitivity.

Treatment liquid Monomethylvaraminophenol sulfate 5gL-ascorbic acid 20gNa, Bo,
Adjust to 12 with 70g water■ Gradation: Density at an exposure amount that is O, iogE higher than the exposure amount that calculated the sensitivity of the sample obtained in Example 1-(5)-, and the exposure amount that calculated the sensitivity. Find the difference in concentration between. The larger this value (ΔD) is, the higher the contrast is, which is desirable in the present invention. in fact.

It is 1.0 based on ΔD of sample 1-1-■,
The ΔD of other samples is shown as a ratio (ΔDr) to the ΔD of sample 1-1-■.

■ Pressure characteristic evaluation method: The obtained film coated sample was
It is bent under conditions where the relative humidity is controlled to 40% at 5°C. This bending is done 1 time along the iron bar with a diameter of 6III11.
Bent 80 degrees. Immediately after this operation, the exposure time is 1/1
00 seconds, exposure amount 2 Wedge exposure with CMS, and the above ■
The same process was performed. As a result, the ratio of the amount of change in fog due to bending to the maximum density ΔF og / D■ and the reciprocal of the exposure amount that gives an optical density of +0.1 fogging as in ■ is defined as sensitivity, and the amount of change in sensitivity due to bending is ΔS was determined.

Relative sensitivity, ΔDr, Δ
The results of evaluating Fog/Da and ΔS are summarized in Tables 2 and 3, respectively.

As can be seen from Table 2, the formation of particles with uniform iodine content includes Fe, Ru, Re, Os having at least two cyanigants according to the present invention.

Even when it is carried out in the presence of metal complexes of Ir, Pt, or Au, the sensitivity is almost always desensitized, and even if it is sensitized, the degree of sensitization is small.

In addition, fog caused by pressure is not improved or is worsened, which is not preferable.

Regarding K 4 [Fe (CN) s ], as a result of investigating the dependence on the amount added, a slight increase in sensitivity and a sharpening of the contrast were observed in samples 1-1-〇 to ■, but fogging due to pressure increased. This is not desirable. On the other hand, the amount added is 3
When it is more than X 10'''Sman/rmoQAg, pressure-induced fogging and sensitization are slightly improved, but the sensitivity is significantly reduced and the tone is softened, so this also did not give favorable results.Sample 1-1- About ■ to ■ 5TE
J by VES, Photgr, Sci Volume 9 3
22 (1961) method to measure internal sensitivity.

Sample 1-1 without addition of metal complex with cyanigant
An increase in the internal sensitivity of the sample to which K4CFe(CN)s] was added relative to -■ was observed, and the degree of increase was greater as the amount of K4[Fe(CN)G] added was larger.

Particles with uniform iodine content are made of Fe, Ru, Re, Os, which have at least two or more cyanigants.

The disadvantage of forming based on a metal complex of Ir, Pt, or Au is thought to be due to this increase in internal sensitivity.

On the other hand, as is clear from Table 3, in contrast to sample l-1-■, sample l-2-■ was introduced with a first coating layer having a molar fraction of silver of 0.02 by iodine substitution. Sensitivity increased, but the tone became slightly softer. In addition, regarding pressure characteristics,
Although fog caused by pressure was significantly improved, this time desensitization caused by pressure occurred, which was not desirable. On the other hand, sample l-2- ■〜0
A significant increase in sensitivity and higher contrast were observed with respect to comparative sample 1-2-■, and pressure characteristics were also improved compared to l-2-■.
In addition to the good pressure-induced fogging properties of 1-2-2, it was found that pressure-induced desensitization, which was a problem with 1-2-■, was greatly improved. These favorable effects are due to K, [Fe(C
This is particularly noticeable in N)G and ni3[Fe(CN),]. Furthermore, when comparing samples 1-1-■ to ■ and samples 1-2-■ to When the second coating layer is provided by iodine substitution.

Even if the amount of the above metal complex added is increased, no desensitization occurs.

In fact, the positive effects were even greater. However, sample 1-2
-■~0, Ru, Re, Os, Ir.

Even if the amounts of Pt and Au compounds added were changed, no further increase in sensitivity was observed. K 4 [F e (CN
)s ] for C-phase silver I X 10-'won
/ mollAg added sample 1-2-■ and Fe(12
, the same < I As a result of comparing the sensitivity, gradation, and pressure characteristics of Sample 1-2-Q to which Ag was added, it was found that the effects of the present invention appear only when a metal complex having a cyanigant is added.

Relative sensitivity, ΔDr, ΔFog/Da, and ΔS were determined using the method defined in Example 1-[5] for samples 1-3-■ to O.
The results of the evaluation are shown in Table 4. Comparing this with the results in Table 2, it was found that even when the B phase of silver iodide was introduced, it had the same effect as when the B phase was introduced by iodine substitution.

Sample in which particles were formed in a relatively high pH atmosphere■-4-■
As a result of similarly measuring the relative sensitivity for and ■, ■-
The relative sensitivity of ■−■ is 120, whereas the relative sensitivity of K, [Fe(
The relative sensitivity of sample 1-4-0 to which CN)-1 was added at a relatively high pH was 95, indicating that it was rather desensitized. In other words, it was found that the effect of the present invention does not appear when a metal complex having a cyanigant is added at a high pH.

(Leaving space below) Example 2 [1] The method for preparing sample 11-1-■ is the same as that of Example 1-[1]-■ until the A phase is formed, but the amount of silver nitrate is 34 g. Physiognomy emulsion, 790 cc of water, 1 gelatin
5g of acetic acid and 4.5mu of acetic acid were mixed in a container kept at 75°C, an aqueous solution 15 containing 134g of A g'
0- and K B r19. o g , and KI6.6
A phase B was formed by simultaneously adding an aqueous solution containing g by a double jet method while keeping the pBr at 2.7. Furthermore, 433 cc of 0.64 NAgNO solution (liquid C) and 1
．． A solution (D solution) in which 3.3 g of KI was added to 433 cc of 09NKBr solution was simultaneously added over 45 minutes by a double jet method while maintaining pBrl at 41 to form C phase. The particles thus obtained had an average diameter of 1.4
It is a monodisperse octahedral particle of 2μ.

When preparing samples ll-1-■ to O, K, [Fe (CN)-].

K3[Fe(CN)G] -K4[Ru(CN)a
ko, KJRe(CN)I], ni4[○s(CN)
G1. K4E I r(CN)G1゜Kz [pt
(CN)sco, K[Au(CNLl 0.01%
The aqueous solution was added in one portion. Example 1 after the chemical sensitization process
- Same as (1).

The particles of samples n-1-■ to O were A with an iodine content of 2 mol%.
Between the A phase and C phase of gBrI, A with an iodine content of 20 mol%
It has a structure in which the B phase of gBrI is sandwiched.

[2] The preparation method for samples 11-2-■ to O is as follows:
．． The preparation was exactly the same as the preparation of Samples 11-1-■ to O described above, except that a solution containing 4 g and 3.3 g of KI was used.

The particles of Samples 11-2-
Between the A phase and C phase of gBrI, A with an iodine content of 10 mol%
It has a structure in which gBrI is sandwiched.

For samples 11-1-■~O and ll-2-■~O,
Example 1-45], the relative sensitivity, ΔDr
, ΔFog/Dffi, and ΔS are shown in Tables 5 and 6, respectively.

As a result of comparing Table 3 and Table 5 in Example 1, it was found that the B phase was not only subjected to the halogen substitution method using iodide ions as in the case of Example 1, but also had a significantly higher content than the A phase. It was found that the same effects as in Example 1, such as higher sensitivity, higher contrast, and improved pressure characteristics, can be obtained by introducing the B phase having a higher contrast ratio. Furthermore, regarding the method of adding metal complexes having at least two cyanigants in the present invention, there is not only a method of adding the metal complexes to the D solution when forming the C phase, but also a method of directly adding an aqueous solution of these metal complexes into the reaction vessel. It was also found that the same effects as in Example 1 can be obtained.

On the other hand, when comparing Table 3 in Example 1 with Table 6 regarding ll-2-■~O, it is found that even if phase B with a relatively low iodine content is introduced, the effect is similar to that in Example 1. It turns out that you can't get it.

In other words, it can be said that the effects of the present invention will not be exhibited unless the silver iodide content of phase B is higher than that of phases A and C to some extent.

(Space below) Example 3 30 g of gelatin, 0.4 g of potassium bromide, and 30 cc of 25% aqueous ammonia were added to water IQ, and in a container kept at 50°C, while stirring, 250 g of silver nitrate per IQ was added.
After simultaneously adding 13 cc of an aqueous solution (liquid A) containing g and 13 cc of an aqueous solution (liquid B) containing 176.4 g of potassium bromide and 5.0 g of potassium iodide per IQ,
To 187 cc of liquid A, liquid B was added at the same time by a potential control method in order to maintain pBr=2.44 (phase A, ie, internal core). Next, 25.5 cc of acetic acid was added, and then a C phase (second coating layer) was provided in the same process as for the A phase, and the iodine content consisting of the A phase and C phase of 1.66μ was reduced to 2.
Monodispersed tetradecahedral grains with a uniform silver iodide content of mol % were obtained. When three-fourths of the amount of gold and silver was added during C phase formation, the metal complex compounds were each added at once in the same manner as in Example 2. The silver halide emulsion thus obtained was optimally chemically sensitized with chloroauric acid salt and sodium thiosulfate. The coating process and subsequent steps are the same as in Example 1-(1). Comparative samples 1-1-2 to O were thus obtained.

Samples m-1-■ to O are 200%
Sample 111-2-■-〇 was obtained in exactly the same manner except that an aqueous solution containing 0.4 g of potassium iodide in cc was added over 20 minutes with thorough stirring.

Samples m-1-■ to O and sample 11 [-2-■ ~◎
For, relative sensitivity, ΔDr, ΔFog/Dm, ΔS
The results obtained are shown in Tables 7 and 8.

Comparing Table 8 with Table 7, it was found that the effects of the present invention were remarkable in the monodisperse tetradecahedral emulsion as in Example 1.

(Left below) Example 4 The amount of 25% ammonia at the time of A phase formation was 3 cc, and as a metal complex compound with cyanigant, [
Sample IV-1-
■~■ and IV-2-■~■ were prepared. Sample mV-
Is is 0.6 from 1-■~■ and IV-2-0~0.
These are monodispersed tetradecahedral particles of μ-carbon.

Relative sensitivity, ΔDr, ΔFog/D m, and Δ
The evaluation of S is summarized in Table 9.

According to Table 9, it was found that the effect of the present invention was remarkable even for emulsions with a relatively small size of 0.89μ.

(Leaving space below) Example 5 ■ Preparation of emulsion A 14% potassium bromide aqueous solution was added to an aqueous solution of 6 g of potassium bromide and 30 g of inert gelatin dissolved in 3.7 Q of distilled water using the double jet method while stirring well. and a 20% aqueous silver nitrate solution were added at a constant flow rate for 1 minute at 55° C. and pBr 1.0 (this addition (1) consumed 2.40% of the amount of gold and silver). Next, an aqueous gelatin solution ( After stirring at 55°C, a 20% silver nitrate aqueous solution was added to a solution with a pBr of 1.4.
Potassium iodide was added at a constant flow rate until reaching 0 (this addition (II) consumed 5.0% of the total silver amount), and an amount of potassium iodide such that the amount of potassium iodide added was 8.3 g. A 20% potassium bromide solution and a 33% aqueous silver nitrate solution were added over a period of 80 minutes by double jet method (this addition (m) consumed 92.6% of the total silver amount). During this time, the temperature was maintained at 55° C. and the pBr was maintained at 1.50. The amount of silver nitrate used in this emulsion was 425 g. Next, after desalting by the usual flocculation method, gold/sulfur sensitization was optimally performed to obtain a comparative tabular AgBrI (AgI= 2.0 mol %) was prepared as comparative sample V-1-■. However, the steps after the coating step are the same as in Example 1-(1).

In comparative sample V-1-■, during addition (m).

When 75% of the amount of gold and silver is consumed, K 4 [F e
Comparative sample V-1-■ was prepared in exactly the same manner except that a 00.1% aqueous solution of (CN)s] was added in an amount of 1X10-s mol to 1 mol silver relative to the amount of gold and silver.

In the preparation procedure for the above comparative sample V-1-■, a solution containing 8.3 g of potassium iodide was added during step (m), when 57% of the amount of gold and silver was consumed, and a solution of silver nitrate and potassium bromide was added. The average particle diameter/particle thickness ratio was 6.3 and the equivalent sphere diameter was 0.8 using the same method except that the addition of
A tabular AgBrI (AgI = 2.0 mol %) of the present invention having μ was prepared, and a comparative sample V-2-■ was bound.

In the above comparative sample V-2-■, K4[Fe(CN
),] 00.1% aqueous solution to the total silver amount
Sample V-2-■ (invention) was prepared in exactly the same manner except that silver was added in an amount of 1 mole silver.

Also for these samples, the relative sensitivity, ΔDr.

As a result of evaluating ΔFog/Da and ΔS, it was found that, as in Example 1, the light-sensitive material using the silver halide emulsion of the present invention had high sensitivity and high contrast, and was also excellent in pressure characteristics.

Example 6 Preparation of Sample VI-1 A multilayer color light-sensitive material consisting of each layer having the following composition was prepared on a cellulose triacetate film support having a thickness of 205 μm and undercoated on both sides of the film, and Comparative Sample VI-1 was prepared.
-1. In addition, sample 1-
The emulsion used in sample IV-4-2 was used as a low-speed blue-sensitive emulsion.

The coating amount of each composition was shown per 1 m of sample.

Regarding silver halide and colloidal silver, the weights are shown in terms of equivalent silver.

1st layer: Haleshigon prevention layer Black colloidal silver 0.25 g Gelatin 1.9 g Ultraviolet absorber U-10.04g Ultraviolet absorber U-20.1g Ultraviolet absorber U-30.1g Ultraviolet absorber U-40.1g Ultraviolet absorber U-60.1g Additive P-10.1g Additive F -100.2g High boiling point organic solvent ○1l-10.1g 2nd layer: Intermediate layer gelatin 0.40g Compound Cpd-DIO■ Dye [ ) -40,4 ■ High-boiling organic solvent Oi1 3 40 mg dye [) -60,1 g 3rd layer: Intermediate layer non-photosensitive fine grain silver iodobromide emulsion (average grain size 0.1 μs, A
gI content 1 mol%) Silver amount 0.15g Fine grain silver iodobromide emulsion with surface and interior covered (average grain size 0
．． 06u! n, coefficient of variation 18%, AgI content 1 mol%)
Silver amount 0.05 g Additive M-10,
05g Gelatin 0°4g 4th layer: Low sensitivity red-sensitive emulsion layer Emulsion A Silver amount 0.2g Emulsion layer O, 3g Additive F
-141■ Gelatin 0.8g Compound Cpd-K O, 05g Coupler C-10, 15g Coupler C-20, 05g Coupler C-90, 05g Coupler C-100, 10g Compound Cpd-D 10 II
Ig additive F-20, 1° high boiling point organic solvent Oil -20, 10g Additive F-1
20.5w: 5th layer: medium-sensitivity red-sensitive emulsion layer Emulsion B Silver amount 0.2g Emulsion C
Silver amount 0.3g Gelatin 0.8gAdditive F-130,05■ Coupler C-10,2g Coupler C-20,05g Coupler C-30,2g Additive F-20,1 and high boiling point organic solvent 0i1-20 .1g 6th layer: High sensitivity red-sensitive emulsion layer Emulsion D Silver amount 0.4g Gelatin 1.1g Coupler C
-30.7 g Coupler C-10.3 g Additive P-10.1 g Additive F-20.1 and 7th layer: Intermediate layer gelatin 0.6 g Color mixing inhibitor Cpd-L 0.05 g Additive F-11 ,5■ Additive F-72,0g Additive Cpd -N O,02
gAdditive M-10.3g Color mixing prevention agent Cpd-K O.05g
Ultraviolet absorber U-10.1g Ultraviolet absorber U-60.1g Dye D-1' 0.02g Dye Dye-60.05g 8th layer: Silver iodobromide emulsion (average Particle size 0
．． 064, coefficient of variation 16%, AgI content 0.3 mol%)
Silver amount 0.02 g gelatin
1.0g additive P-10,
2g Color mixture prevention agent Cpd-J0.1g Color mixture prevention agent Cpd-M O, 05g
Color mixture prevention agent Cpd-Ao, 1g 9th layer: Low-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion with the inside of the grain covered (average grain size 0.1 mm, AgI content 0.1 mol%) Silver amount 0 .05 g emulsion layer Silver amount 0.3 g emulsion layer
Silver amount 0.1g Emulsion G
Silver amount 0.1g gelatin
0.5 g Coupler C-40, 20 g Coupler C-70, 10 g Coupler C-80, 10 g Coupler C-110, 10 g Compound Cpd -B O, 03
g Compound Cpd-E 0.02
g Compound Cpd-F O,02
g Compound CPd-G O,02
g Compound CPd-H0.02g Compound Cpd-D10mg Additive F-50.1°Additive F-30.2mg Additive F-110.5mg High boiling point organic solvent 0i1-20.2g 10th layer: Intermediate green sensitivity Emulsion layer Emulsion G Silver amount 0.3 g Emulsion layer Silver amount 0.1 g Gelatin
0.6 g coupler C-4
0.1g Coupler C-70.1g Coupler C-80.1g Coupler C-110.05g Compound CPd-80.03g Compound Cpd -E O.02
g Compound Cpd-F 0.02
g Compound Cpd -G O,0
5g Compound Cpd-H0.05g Additive F -50.08 ■ High-boiling organic solvent Oil -20.01g 11th layer: High sensitivity green-sensitive emulsion layer Emulsion I Silver amount 0.5 g Gelatin 1.1 g Coupler C- 40.4g Coupler C-70.2g Coupler C-80.2g Coupler C-120.1g Coupler C-9' 0.05g
Compound Cpd-B O, 08g
Compound Cpd-E 0.02g
Compound Cpd-F 0.02g
Compound Cpd-G O,02
g Compound Cpd-H0,02g Additive F -20,3■ High boiling point organic solvent Oil -20,04g Additive F-13
0.05mg 12th layer: Intermediate layer gelatin 0.8g Additive F -12.0■ Additive F -82.0■ Dye D-10.1g Dye D-30.07g Dye D -80.03g Dye D - 20.05g 13th layer: Yellow filter layer Yellow colloidal silver Silver amount 0.1g Gelatin 1.3g Dye D-50
,05g Color mixing prevention agent Cpd-A 0.01
g Additive F -40.3 ■ High boiling point organic solvent 0il - 10.01 g Dye Dye 7 0.03 g Additive M - 20.01 g 14th layer: Intermediate layer gelatin 0.6 g Dye D - 90.02 g 15th Layer: Low-speed blue-sensitive emulsion layer Emulsion J Silver amount 0.4g Emulsion K
Silver amount 0.1g emulsion L
Silver amount 0.1 g gelatin
0.9 g coupler C-130,
1g Coupler C-50.6g Additive F -20.2■ Additive F -50.4■ Additive F -80.05■ 16th layer: Medium-sensitivity blue-sensitive emulsion layer Emulsion L Silver amount 0.2 g Emulsion Amount Silver amount 0.4 g Gelatin 1.2 g Coupler C-1
30.1g Coupler C-50.3g Coupler C-60.3g Additive F -20.04■ Additive F -80.04■ 17th layer: High sensitivity blue-sensitive emulsion layer Emulsion N Silver amount 0.4 g Gelatin 1.4g coupler C
-60,5g Coupler C-140,2g Additive F -20,4■ Additive F -80,02■ Additive F-91■ 18th layer: 1st protective layer gelatin 0.9g Ultraviolet absorber U-10 ,04g Ultraviolet absorber U-20,01g Ultraviolet absorber U-30,03g Ultraviolet absorber U-40,03g Ultraviolet absorber U-50,05g Ultraviolet absorber U -60,05g High-boiling organic solvent Oil -10, 02g formalin scavenger Cpd-G O, 2gCP
d-IO, 4g Latex dispersion of ethyl acrylate o, os g Dye D-30, 05g Additive Cpd-J 0.02g
Additive F -11,0■ Additive Cpd -N O,01
g Additive F-61, Oq Additive F-70, 5 g Additive M-20, 05 g 19th layer: 2nd protective layer colloidal silver Silver amount 0.1 ■ Fine grain silver iodobromide emulsion (average grain size 0. 06 kon, AgI content 1 mol%) Silver amount 0.1 g gelatin
0.7 g 20th layer: Third protective layer Gelatin 0.7 g Polymethyl methacrylate (average particle size 1.5.) 0.1 g 4=6 copolymer of methyl methacrylate and acrylic acid (average particle size 1.5. 5um) 0.1 g silicone oil 0.03 g surfactant W-13,Q.

Surfactant W-20,03g 21st layer (back layer) Gelatin to g Ultraviolet absorber U-10,05g Ultraviolet absorber U-20,02g High boiling point organic solvent Oil -10,01g 22nd layer (back protective layer ) Gelatin 5 g Polymethyl methacrylate (average particle size 1.5.) 0.03 g 4:6 copolymer of methyl methacrylate and acrylic acid (average particle size 1.5 μs) 0.1 g Surfactant W-11q Surfactant W-210 Additive F-1 was added to each silver halide emulsion layer.

In addition to the above composition, each layer also contained gelatin hardening agent H-1.
Then, coating surfactants W-3 and W-4 and emulsifying surfactant W-5 were added.

Furthermore, phenol 1,2-penzisothiazolin-3-one, 2-phenoxyethanol,
Phenyl isothiocyanate and phenethyl alcohol were added.

The structural formulas of the compounds used in this example are shown in Table 8 below.

The silver iodobromide emulsion used in sample VI-1 is as follows.

(Left below) Emulsion base Grain characteristics Average grain size Coefficient of variation AgI content) (%) (%) A Monodispersed tetradecahedral grains 0.35
16 4.5B Monodisperse cubic internal latent image type particles
0.45 10 5. OC monodispersed tetradecahedral particles 0.60 1g
4. OD polydisperse twin grains 1.10
25 3. OE monodispersed cubic particles
0.30 17 4. OF Monodispersed cubic particles 0.40 16
4.0G Monodispersed cubic internal latent image type particles 0.50
11 4.5H monodisperse tetradecahedral particles
0.65 9 3.5 engineering Polydisperse tabular grains, 1.20 28
3.0 Average aspect ratio 5.3 J Monodisperse tabular grains, 0.70
18 4.5 Average aspect ratio 3.8 K Monodispersed tetradecahedral particles 0.60
17 2. OL Monodisperse octahedral particles
0.80 14 4.0M Monodisperse tabular grains, 1.00 18
4.0 Average aspect ratio 4.5 N Monodispersed tetradecahedral particles 1.45
14 Spectral sensitization of 2.0 emulsion A-N S-10,025 Immediately after chemical sensitization 5-20.25 Immediately after chemical sensitization CS-10
,02 Immediately after chemical sensitization S -90,002 Immediately after chemical sensitization S -20,25 Immediately after chemical sensitization DS-10,01 Immediately after chemical sensitization 5-20.10 Immediately after chemical sensitization S -70
,01 Immediately after chemical sensitization ES-30,5 Immediately after chemical sensitization S-100,
05 Immediately after chemical sensitization 5-40.1 Immediately after chemical sensitization F
S-30,3 Immediately after chemical sensitization 5-40.1
Immediately after chemical sensitization G S-30,25 Immediately after grain formation S -40,08 Immediately after grain formation HS-30,2 During grain formation S -100,1 Immediately after chemical sensitization S-40,06 During grain formation IS -30,3 Just before the start of chemical sensitization -40
, 07 Just before the start of chemical sensitization 5-80.1 Just before the start of chemical sensitization J
S-50, 2 grains forming S -60,05 grains forming KS-50, 2 grains forming S -60,05 grains forming L S-50,22 Immediately after grain formation S -6
0.06 Immediately after grain formation S-50,15 Immediately after chemical sensitization S-60,
04 Immediately after chemical sensitization N5-50.22 Immediately after grain formation S
Comparative sample VI-1 was prepared in exactly the same manner as Comparative sample VI-1 except that the emulsions used in Samples 1-2-■ and Summer-2-■ were used as emulsion N immediately after the -60,06 grain formation was completed. and sample VI-3 was prepared. Furthermore, Comparative Samples VI-4 and VI-5 were prepared in the same manner as Sample VI-3 except that the emulsions used in Samples 2-2-2 and IV-2-2 were used as emulsions.
was created.

Sensitivity, pressure characteristics, and graininess of samples VI-1 to VI-5 thus obtained were measured by the methods defined below.

■Sensitivity: After applying a wedge exposure of 1/100 seconds to the sample piece at 2GMS and performing the following development process, sensitometry is performed using a blue filter, and the density is 0.2 large from the minimum yellow density. The reciprocal of the exposure amount corresponding to the density was defined as the highlight sensitivity (S,...) of the blue photosensitive layer. Similarly, the shadow sensitivity of the blue photosensitive layer (S2.
. ) was sought. The actual sensitivity is S of sample Vl-1. ,2
゜S2. . are each set to 100, and the sensitivity of other samples is
Which ratio is the relative sensitivity S rO + 215r, .

It was expressed as

Processing process first development (black and white development) 38℃ 75 seconds water washing
38℃ 90 seconds reverse exposure 1001ux or more 60 seconds or more color development 38℃ 135 seconds water washing 38℃ 45 seconds bleach fixing 38℃ 120 seconds water
Wash 38℃ 13
Dry for 5 seconds Composition of processing solution (first developer) Nitrilo-N,N,N-trimethylenephosphonic acid, pentasodium salt 0.6 g Diethylenetriaminepentaacetic acid, pentasodium salt 4.0 g Potassium sulfite 30.0 g Thiocyanide Potassium acid 1.2g Potassium carbonate
35.0 g Hydroquinone monosulfonate potassium salt 25.0 g Diethylene glycol 15.0 aQl-phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone 2.0 g Potassium bromide 0.5 g Potassium iodide 5.0 ■ Water plus
1Q (pH 9,70) (Color developer) Benzyl alcohol 15.0 Diethylene glycol 12.0 d3.
6-Sithia 1,8-octanediol 0.2 g Nitrilo-N,N,N-)-rimethylenephosphonic acid, pentasodium salt 0.5 g Diethylenetriaminepentaacetic acid, pentasodium salt 2.0 g Sodium sulfite 2.0 g Carbonic acid potassium
25.0 g Hydroxylamine sulfate 3.0 g N-ethyl-N-(β-
Methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 5.0g Potassium bromide 0.5g Potassium iodide
1.0■ Add water
IQ (pH 10,40) (Bleach-fix solution) 2-Mercapto-1,3,4-triazole 1, Og Ethylenediaminetetraacetic acid disodium disodium salt
5. Og ethylenediaminetetraacetic acid/Fe(nl)/ammonium hydrate
80. Og Sodium Sulfite 15
．． 0 g sodium thiosulfate (700g/Q liquid)
160.0 d glacial acetic acid
5.0-Add water IQ
(PH6,50) ■Pressure characteristic evaluation method: The obtained film coated sample was heated at 25°C.
Bend it under conditions where the relative humidity is controlled to 40%. This bend was made by 180° along a 6 m++ diameter iron bar. Immediately after this operation, wedge exposure was performed at an exposure time of 1/100 seconds and an exposure amount of 2 CMS, and the same processing as above was performed. From this result, the maximum density change due to bending (ΔFog), ΔS0.2, respectively.
and ΔS2. .

So, 2 and S2. . The amount of change in sensitivity due to bending was determined.

(2) Graininess The yellow image was exposed to white light using a two-step wedge, and the graininess of the yellow image was measured using a conventional RMS method using blue light. The measurement aperture is 48um and the concentration is 0.5.
and the RMS value at a concentration of 2.0. Concentration 0
．． RMS corresponds to 5. , S, corresponding to density 2.0 is RMS, . Closed. The smaller the RMS value, the better the graininess. Actually, the RMS of sample VI-1
,, RMS2,. Assuming that the value of is 1.0, the other samples have relative values RMSP, , , RMS, □, ,
Expressed as

VI-1 to 6 SFo, 2, SF3. O1ΔFog, △
S Q , 2, ΔS2. . , RMSP, , RMSP□
,. The values are shown in Table 10.

Results 1: The light-sensitive material containing the silver halide emulsion of the present invention subjected to color reversal processing had a
It was found to have high sensitivity and excellent pressure resistance. Furthermore, it has been found that when the silver halide emulsion of the present invention is used in a high-sensitivity layer, the graininess of the highlight area is improved despite the grain size being the same. In addition to this, it was unexpected and surprising that when the silver halide emulsion of the present invention was used in the low-speed layer, it was possible to improve the grain shape of some of the shadows even though the grain size was the same. Met.

(Left below) Example 7 On an undercoated cellulose triacetate film support,
Comparative sample 1-1, which is a multilayer color light-sensitive material, was prepared by applying layers having the compositions shown below. The emulsion used in Sample 1-1-■ was used as a red-sensitive high-sensitivity emulsion.

(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, for sensitizing dyes, the coating amount is expressed in moles per mole of silver halide in the same layer.

(Sample ■-1) 1st layer (antihalation layer) Black colloidal silver Silver 0.18 Gelatin 1.40 2nd layer (intermediate layer) 2.5-di-t-pentadecylhydroquinone 0.18E
-10,070 EX -30,020 EX-12'2.0X10-'
U -10,060 U-20,080 U -30,10 HB S -10,10 HB S -20,020 Gelatin 1.04 3rd layer (first red-sensitive emulsion layer) Emulsion A Silver 0.25 Emulsion B
Silver 0.25 Sensitizing dye 1
6.9 X 10-' Sensitizing Dye I
I 1.8 X 10-' sensitizing dye m3. lX10-' EX-20,34 EX-100,020 U-10,070 U2 0.050U
-30,070 HB S -10,060 Gelatin 0.87 4th layer (second red-sensitive emulsion layer) Emulsion G l! 1.00
Sensitizing dye I5゜I X 10-5 Sensitizing dye II 1.4 X 1
0-' Sensitizing dye DI 2.3
X 10-'E X -20,40 E X -30,050 E Layer) Emulsion D Silver 1.60 Sensitizing Dye 1 5.4 X 10-5 Sensitizing Dye If 1.4 X 10-
5 sensitizing dye m 2.4 X 1
0-'EX -20,097 EX -30,010 EX 4 0.
080HB S -10,22 HBS -20,10 Gelatin 1.63 6th layer (intermediate layer) EX -50,040 HB S -10,020 Gelatin 0.80 7th layer (first green-sensitive emulsion layer) Emulsion A Silver 0.15 Emulsion B
Silver 0.15 sensitizing dye IV
3. OX 10-'sensitizing dye y 1. OX 10-' Sensitizing dye VI 3.8 X 10-'
E X -10,021 E X -60,26 E X -70,030 E ) Emulsion C Silver 0.45 Sensitizing Dye IV 2. I
o-S sensitizing dye V7. OX
10-' Sensitizing dye VI 2.6
X 10-'EX -60,094 EX -70,02S EX -80,018 HB S -10,16 HB S -38,0 ) Emulsion E Silver 1.20 Sensitizing dye IV 3.5 X 10-'
Sensitizing dye V8. OX 10-
'Sensitizing dye VI 3. OX1
0-'E X -10,02S E X-110,LO E
Layer (yellow filter layer) Yellow colloidal silver silver o, os.

EX -50,080 HB S -10,030 Gelatin 0.95 No. 11
Layer (first blue-sensitive emulsion layer) Emulsion A Silver 0.080 Emulsion B Silver 0.070 Emulsion F
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 G Silver 0.45 Sensitizing dye■ 2. I X 10-'E
X -90,1S E X-107,OX 1O-3 HB S -10,050 Gelatin 0.78 No. 13
Layer (third blue-sensitive emulsion layer) Emulsion H silver 0.77 Sensitizing dye ■ 2.2 X 10-
'EX -90,20 HB S -10,070 Gelatin 0.69 No. 14
Layer (first protective layer) Emulsion■ Silver 0.20U -
40,11 U -50,17 HB S -15,0X10-” Gelatin i, o.

15th layer (second protective layer) H-10,40 B-1 (diameter 1-7) 5.0xl
O-2B-2 (diameter 1゜7tna) o, 1゜B -3
0,1O 5-10,20 Gelatin 1.20 Furthermore,
W-1, 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-
10, F-11, F-12, and F-13.

The structural formulas of the compounds used here are shown in Table 0 below, and the emulsions are shown below.

(Left below) Samples rV-1-■, rV-2-■, ■-2 as emulsion H
- Comparative sample -2, comparative sample -3, and sample -4 (invention) were prepared in exactly the same manner as comparative sample -1, except that the emulsion used in -2 was used.

The sensitivity and pressure characteristics of the samples (1) to (4) thus obtained were evaluated by the method defined below.

Sensitivity: After applying a wedge exposure of 1/100 seconds to the sample piece with an exposure dose of 2 CMS and performing the following development process, sensitometry was performed using red light, and the density was 0.2 large from the minimum density of cyan. The reciprocal of the exposure amount corresponding to the density was defined as the sensitivity. In reality, the sensitivity of sample ■-1 is set as 100,
The other samples were compared by determining their relative sensitivities with sample 1-1.

(Left below) Processing method Step Processing time Processing temperature Color development
3 minutes 15 seconds 38℃ bleaching 6
Minutes 30 seconds 38℃ water washing 2
Minutes 10 seconds 24℃ fixation 4
Minute 20 seconds 38℃ water wash 0 1 minute 05 seconds 24℃ water wash ■ 1 minute OO seconds 2
Stable at 4℃ 1 minute 05 seconds 38
Drying at ℃ 4 minutes 20 seconds 55℃
Next, the composition of the treatment liquid will be described.

(Color developer) (Unit g) Diethylenetriaminepentaacetic acid 1.01-Hydroxyethylidene-1,1-diphosphonic acid 3.0 Sodium sulfite 4.0 Potassium carbonate
30.0 Potassium Bromide
1.4 potassium iodide
1.5゜Hydroxylamine sulfate
2.4-[N-Ethyl-N-β-hydroxyethylamino]-2-methylaniline sulfate 4.5 Add water 1. OQp H10,05 (Bleach solution) (Unit g) Ethylenediaminetetraacetic acid ferric sodium trihydrate 100.0 Ethylenediaminetetraacetic acid disodium salt 10.0 Ammonium bromide 140.0 Ammonium nitrate 30.0 Aqueous ammonia (27%)
6.5 d Add water
1. OQp H6,0 (Fixer) (Unit g) Ethylenediaminetetraacetic acid disodium salt 0.5 Sodium sulfite 7.0 Sodium bisulfite 5.0 Ammonium thiosulfate aqueous solution (70%) 170.0 d Add water
1.0Qp H6,7 (stabilizing liquid) (unit g) Formalin (37%) 2.0 mN polyoxyethylene-P-thousand nononylphenyl ether (average degree of polymerization 10) 0.3 Ethylenediaminetetraacetic acid disodium salt 0 Add .05 water 1. OQp H5,0-
8,0 Pressure characteristics: 2g + 4g + 6 of the sample before irradiation
5 c using a sapphire needle (radius of curvature of the needle tip 0, 1 m) with a load of 8 g and 8 g.
After scratching at a speed of 7 seconds and then exposing to light, the above-mentioned treatment was performed to examine whether or not sensitization occurred.

(See margins below) Evaluation Degree of desensitization xx Sensitization or desensitization is observed from a load of 2 g.

× Load 4g △　　　　Load 3g O load 8g No desensitization was observed even at an O load of 8 g.

Table 11 shows the results of comparing the relative sensitivity and pressure characteristics of Samples -1 to -4 using the above method.

Comparing these results, it was found that the light-sensitive material using the silver halide emulsion of the present invention has high sensitivity and excellent pressure characteristics.

Table 11 Table A [Fs(CN)J ”- [Fs(CN), Fl 3- [Fa(CN)-Fx]”- [Fa(CN)sCIl]”- [Fe(CN)-C4, 1- [Fe(CN)s Brl 3- [Fe(CN)4Br,] ” [Fe(CN)s(OCN)] '- [Fe(CN), (SCN)] ”- [Fe(CN) s(N3)] ]' -CF6CCNM(H2O)]3- [Fe(CN)Gco0- [Fe(CN)s Fl'- [Fe(CN), FJ'- 1''Fe(CN), Cjl ]'- [Fe(CN), C4 6- [:Fe(CN)s Br,]'- [Fe(CN)-(OCN) 4- CFe( CN)s(SCN)] '- [F1! I(CN)S(N3)] '-[Fs(CN)
s(HsO) 4- [Ru(CN)s 4- [Ru(CN), Fl 4- [Ru(CN)4 F2 ] '- [Ru(CN)s CjD'- [Ru(CN), C&1'- [Ru(CN), Brl a- [Ru(CN)4Br2ko4- [Ru(CN), I]'- CRu(CN)41zko4-[Ru(CN)s(OCN)]' - [Ru(CN), (SCN)]'- [Ru(CN)i CN5)ko 6 [Ru(CN)s (H2O)ko 3-[Re(CN)
sl'-[Re(CN)sF]'-[Re(CN)4t,]'-[Re(CN),Cl21'-[Re(CN)4C4]'-[Re(CN)i Brco 4- [Re(CN)4Bra] '- [:Re(CN),I] '- [Re(CN)4Is] '- rOs(CN)sco4- C05CCN), Fl'- [Qs(CN)4F! ] '- [0s(CN), Ca,] '- (Os(CN)4CQ2ko 4- [0s(CN), Brl'- [0s(CN)4Br,]'- [0s(CN)s r ] '- [0s(CN)41.'l '- [0s(CN), (OCN)]'- [0s(CN), (SCN) 4- [Os(CN)g (Na)] '- [ ○5(CN), (H2O)] ”- [Ir(CN)sl ”- [Ir(CN3.Cai'- [:Ir(CN)4C&]”- CIr(CN), Brl ”- [Ir( CN)4Br-] ”- [Ir(CN input Iko1- [Ir(CN)+IJ ”- [1r(cN)s(Ni)] ”- [:Ir(CN)s(HsO)]”- [Pt(CN),] ” [Pt(CN), Cchi] 2- cPt(cN)4Br*]”- [Pt(CN), Ll ”- [Au(CN), co- [Au(CN) , Cgsl - Table 8 H H H C-5 QC,H.

H H C-12 CH2 ■ C(l y/z=I CH.

○11-1 Dibutyl phthalate 0i1-2 Tricresyl phosphate pd-A H H pd-B Pd-C pd-D H pd-E pd-F pd-G pd-H pd-I CH.

H U-2 (t)C4Hs o3K Separate, Na αnH D-7 C) l, =CH5O, CH2C0NHCH.

sadness CH2=C)tso,CH,C0NHC)I.

CH2 C,F17502 NCH2C00K C□H7 CH,C00CH,CH (Cx8%)C4H1NaO,
5-C) ICOOCR,CH(C,H,)C,H.

→ZH, -CH)- ■ C0NHC4H, (t) 70, -CH← " ωkaku, H9 H ″%Nノ F-6 H H CH.

Table 6 X-1 0g X-2 H X-3 H X-4 0H X-5 CtHz3(n) X-6 X-7 Q X-8 CH, CH.

I X-9 X-10 H CI+ X-12 X-13 U-4
Tricresyl phosphate HBS-2 di-n-butyl phthalate (t) CsHxx ω2H sensitizing dye I Sensitizing dye ■ Sensitizing dye ■ Sensitizing dye ■ Sensitizing dye ■ Sensitizing dye ■ CH.

I CH,=CH-5o, -C)I2-CONH-C)+2
C12=CH-5O, -CH, -CON)I-CH.

B-1 CH3CO.

-I -I H

Claims (2)

[Claims] (1) In a silver halide photographic material having at least one light-sensitive silver halide emulsion layer on a support, the silver halide layer is made essentially of silver bromide or silver iodobromide. a first coating layer substantially consisting of silver iodobromide provided on the outside of this inner core, and further provided on the outside of the first coating layer substantially consisting of silver bromide or silver iodobromide. containing surface latent image type silver halide grains having a second coating layer consisting of, wherein the silver iodide content of the first coating layer is about 10 mol% or more higher than the silver iodide content of the inner core, The proportion of silver halide in the first coating layer relative to the entire grain is about 0.01 to 40 mol %, and the grain has at least two cyanigants, the following general formula [C-1] or A silver halide photographic material comprising a metal complex represented by [C-2]. [M_1(CN)_6_-_aLa]^n[C-I]
[M_2(CN)_4_-_bLb]^m[C-II](
In the formula, M_1: Fe, Ru, Re, Os, Ir or PtM
_2: Pt or Au L: Ligand other than CN a: 0, 1 or 2 b: 0, 1 or 2 n: -2, -3 or -4 m: -1 or -2) (2) The silver halide photographic material according to claim (1), which contains surface latent image type silver halide grains containing an Fe compound having at least four cyanigants.