JPH0820694B2 - Silver halide photographic emulsion - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a silver halide photographic emulsion. Particularly, it relates to a silver halide emulsion comprising a dispersion medium and tabular silver halide grains.

(Prior Art) Various pressures are generally applied to a photographic light-sensitive material coated with a silver halide emulsion. For example, a negative film for general photography is bent or pulled for frame advance when it is rolled up in a cartridge or loaded in a camera.

On the other hand, sheet-like films such as printing photographic materials and direct medical X-ray photographic materials are handled directly by hand,
Breaking and bending often occur.

In addition, all photosensitive materials are subjected to great pressure during cutting and processing.

As described above, when various pressures are applied to the photographic light-sensitive material, pressure is applied to the silver halide grains by using gelatin as a support (binder) of silver halide grains or a plastic film as a support medium. When pressure is applied to the silver halide grains it is known to vary the photo-sensitive material photographic properties occurs, for example, KBMather, J.Opt.Soc.Am., 38 .10
54 (1948) .P.Faelens and P.de Smet.Sci.et Ind.Pho
t., 25 .No.5.178 (1954) P.Faelens.J.Phot.Sci. 2 .105
(1954).

Therefore, it is strongly desired to provide a photographic light-sensitive material that does not affect the photographic property under these pressures.

As a means for improving the pressure characteristics, a method of containing a plasticizer such as a polymer or an emulsion, or a method of reducing the silver halide / gelatinization of a silver halide emulsion to prevent the pressure from reaching the grains Things are known.

For example, UK Patent 738,618 has heterocyclic compounds, 738,637 has alkyl phthalates, 738,639 has alkyl esters, U.S. Pat. JP-A-49-5017 discloses a method of using paraffin and a carboxylate, and JP-B-530-28086 discloses a method of using an alkyl acrylate and an organic acid.

However, since the method of adding a plasticizer lowers the mechanical strength of the emulsion layer, there is a limit to the amount that can be used, and increasing the amount of gelatin causes a drawback such as a slower phenomenon processing speed. However, it is difficult to achieve a sufficient effect.

On the other hand, in recent years, the sensitivity and the small format of silver halide sensitizer materials have advanced, and photographic light-sensitive materials having higher sensitivity and excellent image quality have been strongly desired.

For this reason, demands for silver halide emulsions for photography are becoming more and more stringent, and there is a higher standard requirement for photographic performance such as high sensitivity, high contrast, excellent graininess and sharpness. On the other hand, a tabular grain manufacturing method and use technique intended for improving sensitivity including improvement of color sensitizing efficiency by a sensitizing dye, improving sensitivity / granularity relationship, improving sharpness and improving covering power are US patents. 4,386,156, 4,504,570, 4,47
No. 8,929, No. 4,414,304, No. 4,411,986, No. 4,400,463
No. 4,4,14,306, 4,439,520, 4,433,048,
4,434,226, 4,413,053, 4,459,353, 4,4
90,458 and 4,399,215.

Generally, spherical silver halide grains such as hexahedrons, octahedrons and potatoes are less susceptible to deformation by external force due to their morphology than tabular grains having a large diameter / thickness ratio. Therefore, there are cases where even the above-mentioned means for improving the pressure characteristics, which are difficult to achieve sufficient effects, can improve the pressure characteristics to a sufficiently satisfactory level, although not sufficient.

However, in general, tabular grains having a large diameter / thickness ratio are remarkably weak against external force due to their shape, and satisfactory pressure characteristics cannot be obtained by the above method.

For example, when silver nitrate is added to a solution containing gelatin, potassium bromide and potassium iodide to form tabular silver halide grains,
A photographic emulsion showing a marked decrease in sensitivity to pressure,
It is extremely inconvenient for practical use. On the other hand, the characteristic of desensitizing to such a pressure is that pure silver bromide grains, or a halogen composition formed by adding a solution of a silver nitrate solution and a halide by the double jet method so as not to re-nucleate the whole grain. The silver iodobromide grains that are completely uniform over the entire area are improved, but on the contrary, the grains are remarkably fogged against pressure, which is also not practically preferable.

U.S. Pat. No. 2,592,250 discloses emulsion grains obtained by subjecting silver chloride emulsion grains to halogen conversion with bromide or iodide ions. Japanese Examined Patent Publication (Kokoku) No. 36978/1975 discloses a method of using an emulsion in which the surface of the above emulsion is chemically sensitized. Japanese Patent Laid-Open No. 61-122641 discloses an emulsion obtained by subjecting an emulsion containing chloride ion to halogen conversion by bromide ion or iodide ion in the presence of a solvent. JPA
No. 51-2417 discloses a method of growing silver halide grains by adding a bromide ion or an iodide ion to a silver chloride emulsion within 20 minutes after the grain formation to perform physical ripening.

However, with such a method for preparing emulsion grains, it is impossible to control grain formation, and as described in the patent, changing the halogen causes the grain size and shape to be completely different. . Therefore, such a technique is difficult to apply to tabular grains.

Japanese Examined Patent Publication No. 61-31454 discloses a method of depositing silver bromide on silver chloride grains in a laminated type rather than a halogen conversion type. U.S. Pat. No. 4,495,277 discloses a silver halide emulsion having a silver chloride layer in one layer of the inner core of a silver halide grain.

JP-A-58-111936 and U.S. Pat. No. 4,414,306 disclose a method of obtaining silver chlorobromide tabular grains by growing silver chlorobromide in the annular region of silver bromide tabular grains.
The tabular grains thus obtained have the characteristics originally possessed by silver chloride, such as the fast development characteristics of silver chloride, as described in the specification, but are improved in the relationship of sensitivity / graininess. Originally, the properties of silver iodobromide are lost.

JP-A-60-258536 discloses silver halide grains containing iodide ions locally. US Patent 4,
No. 210,450 discloses a method for producing silver halide grains whose halogens are changed by iodide ions during grain formation. JP-A-59-99433 discloses that pressure characteristics are improved by providing a high-coide layer inside the tabular grains. JP-A-61-14636 discloses that the pressure property is improved by making the iodide content in the central region of tabular grains higher than that in the outer region.
JP-A-62-54640 discloses a method of introducing a transition line into the annular region of tabular grains by iodide ion. However, the method using iodide is limited in its use because it significantly affects photographic characteristics such as developability at the same time as improving the pressure characteristics.

(Problems to be Solved by the Invention) An object of the present invention is to provide an emulsion comprising silver halide grains having improved sensitivity, high sensitivity and good granularity, which have improved pressure characteristics.

Another object of the present invention is to simultaneously achieve an improvement in sensitivity including an improvement in color sensitization efficiency by a sensitizing dye, an improvement in sensitivity / granularity relationship, an improvement in sharpness, and an improvement in covering power and an improvement in pressure characteristics. To provide a silver halide emulsion.

Another object of the present invention is to improve the above-mentioned performance in an emulsion comprising tabular grains.

(Means for Solving Problems) The above objects of the present invention can be achieved by the following means. That is, in a photographic emulsion containing silver bromide-based grains, the grains have a silver bromide-based layer inside the grains, and a silver chloride- or silver citrate-containing layer thereon.
The silver chloride or silver citrate-containing layer is a silver halide photographic emulsion characterized in that after the layer is formed, a part of the layer is changed to halogen, and further a silver bromide-based layer is further formed thereon. Could be achieved by. Here, the silver bromide-based grains mean that silver bromide is contained in an amount of 40 mol% or more, preferably 50 mol% or more, and most preferably 60 mol% or more.

Deposition of a silver salt having a higher solubility than silver bromide is performed after forming grains substantially consisting of silver bromide. The volume of the grains essentially consisting of silver bromide serving as the base is preferably 5% or more of the volume of the final grains. More preferably 10
%, And most preferably 20% or more. Further, it is preferable that the amount of the grains essentially consisting of silver bromide as the base is within 95% of the volume of the final grains. It is more preferable to occupy 90% or less, most preferably 85% or less. Only when these conditions are satisfied, changes in particle size and shape in the subsequent halogen changing process can be minimized. The underlying grains consist essentially of silver bromide. Substantially silver bromide means that bromide ions are contained in an amount of 40% or more, more preferably 50% or more, and most preferably 60% or more. If this condition is satisfied, the base grain may be any of silver bromide, silver iodobromide, silver iodochlorobromide and silver chlorobromide. The case where iodide ions are contained is remarkably effective in the present invention, preferably 0.5
% Or more, more preferably 1% or more, and further preferably 2
% Or more is desirable.

The base silver halide grains are preferably tabular grains, particularly tabular grains having an aspect ratio of 2 or more. Here, the tabular grains are a general term for grains having one twin plane or two or more parallel twin planes. In this case, the twin plane refers to the (111) plane when ions at all lattice points on both sides of the (111) plane are in a mirror image relationship. When viewed from above, the tabular grains have a triangular shape, a hexagonal shape, or a rounded circular shape.The triangular shape is a triangular shape, the hexagonal shape is a hexagonal shape, and the Have circular outer surfaces parallel to each other. Hereinafter, the present invention will be described by taking the case of using tabular grains as a substrate as an example.

After forming the tabular grains consisting essentially of silver bromide, a silver salt having a higher solubility than silver bromide is deposited.
Such silver salts have a solubility in water greater than that of silver bromide and a solubility in 100 ml of water at 20 ° C. of about 0.02 g, preferably less than about 0.0002 g. Useful silver salts having a higher solubility than silver bromide include, for example, silver halide chloride and silver citrate.

Examples of the halosilver chloride include silver chloride and silver chlorobromide, silver chloroiodide or silver chloroiodobromide having a silver chloride content of 10 mol% or more, preferably 60 mol% or more.

The silver salt having a higher solubility than silver bromide is preferably silver halochloride, particularly silver chloride or silver chlorobromide having a silver chloride content of 60 mol% or more, silver chloroiodobromide, and particularly preferably silver chloride.

Deposition of these silver salts on tabular grains consisting essentially of silver bromide can also be accomplished by the addition of an aqueous silver nitrate solution and an appropriate alkali metal salt (e.g. potassium chloride, potassium citrate in water, separately or simultaneously). The silver bromide, silver iodide, or silver iodobromide can be deposited in parallel with the deposition of a silver salt having a higher solubility than silver bromide. It is also possible to deposit an appropriate amount.

The silver salt, which has a higher solubility than silver bromide, is preferably deposited in an amount of 80 mol% or less in terms of silver amount with respect to the underlying tabular grains. It is more preferably 60 mol% or less, particularly preferably 40 mol% or less, and most preferably 30 mol% or less. Further, the deposition of a silver salt having a higher solubility than silver bromide is preferably 1 mol% or more in terms of silver amount with respect to the base tabular grains. It is more preferably at least 2 mol% and even more preferably at least 3 mol%.

Only when such conditions are satisfied, it is possible to minimize the change in the grain size and shape of the tabular grains during the subsequent halogen change process, and at the same time, achieve the improvement of the pressure characteristics aimed at by the present invention. be able to. Deposition of silver salts having a higher solubility than silver bromide usually occurs in the plane direction of the underlying tabular grains rather than in the ring direction. Preferably, the deposition in the surface direction is effective for the present invention.

For example, when the content of bromide or iodide ions in the silver chloride layer is 60% or less for the deposition of silver chloride in the plane direction, all pAg (logarithm of the reciprocal of the silver ion concentration in the reaction solution) region It is possible to deposit at.

After depositing a silver salt having a higher solubility than silver bromide, substantially silver bromide is deposited through a halogen conversion method. Substantially silver bromide means that bromide ions are contained in an amount of 40% or more, more preferably 50% or more, and most preferably 60% or more. Furthermore, the chloride ion must be less than the chloride content of the layer undergoing halogen conversion. If this condition is satisfied, halogen change is bromide ion,
Iodide ions, chloride ions and mixtures thereof are possible. It can be carried out by adding the above-mentioned halide ion to this halogen change and aging.

That is, in order to convert a silver salt having a higher solubility than silver bromide into a halogen by adding an aqueous halogen solution, it is preferable to add potassium bromide, potassium iodide or a mixture thereof. At this time, the halogen aqueous solution may contain an appropriate amount of sodium chloride.

On the other hand, in order to further deposit silver halide on a silver salt having a higher solubility than silver bromide to convert it into halogen, the silver halide to be deposited is silver bromide, silver iodide or silver iodobromide. preferable. At this time, a suitable amount of silver chloride may be contained as the silver halide to be deposited.

The conditions for deposition vary depending on the temperature, the deposition rate and the halogen composition of the deposited silver halide, but at 50 ° C pAg 7.5 or more, preferably 8.0 or more, more preferably 8.5 or more, and at 75 ° C pAg 7 or more, preferably 7.5. Or more, more preferably 8.0 or more.

At temperatures between 50 ° C. and 75 ° C., pAg values in the middle of this pAg region are preferred.

The deposition rate is preferably equal to or lower than the critical growth rate, and particularly preferably equal to or lower than 1/2 of the critical growth rate.

As a method for depositing silver halide, a method of adding an aqueous solution of silver nitrate and an aqueous solution of halide or a method of adding fine grain silver halide is preferable.

The silver nitrate aqueous solution may be added after the addition of the halide aqueous solution or at the same time.

Halogen conversion as used herein does not mean that all silver salts having a higher solubility than silver bromide are replaced by silver bromide. Preferably 5% or more, more preferably
It is preferred that a silver salt having a solubility of 10% or more, and most preferably 20% or more higher than silver bromide is substantially replaced by silver bromide. The degree of this halogen conversion can be easily known by comparing the deposited amount of a silver salt having a higher solubility than silver bromide with the analyzed content of a highly soluble silver salt after the halogen conversion. For example, X-ray diffraction, EPMA (also called XMA) method (a method for detecting silver halide composition by scanning silver halide grains with an electron beam), ESCA (also called XPS) method (X This can be confirmed by combining a method of irradiating a ray and separating the photoelectrons emitted from the particle surface).

The most preferred form of the present invention can be achieved by further depositing a silver salt and growing grains after undergoing halogen conversion. This grain growth is accomplished by adding silver, bromide, iodide and chloride ions to the reaction vessel according to well known techniques. The size distribution of the tabular grains formed in accordance with the present invention is also influenced by the size distribution of the tabular grains consisting essentially of silver bromide on which the silver salt having higher solubility than silver bromide is deposited. However, it is greatly influenced by the conditions for growth of tabular grains after halogen conversion, that is, the bromide salt and iodo salt concentrations at the growth stage.

If the pBr is too low, tabular grains having a high aspect ratio are formed, but the coefficient of variation of the projected area becomes significantly large.
By maintaining the pBr between about 2.2 and 5, tabular grains having a small variation coefficient of the projected area can be formed.

Provided that the above pBr condition is satisfied, silver,
The concentration and the introduction rate of the bromide and iodine salt may be the same as those conventionally used. Silver and halide salts are desirably introduced at a concentration of 0.1 to 5 moles per liter, but a wider range of concentrations conventionally used, for example, from 0.01 moles per liter to saturation can be employed. A particularly preferred precipitation technique is
The purpose is to increase the rate of introduction of silver and halide salts to reduce the time of precipitation. The introduction rate of silver and halide salts can be increased by increasing the introduction rate of the dispersion medium and silver and halide salts, or by increasing the concentration of silver and halide salts in the introduced dispersion medium. By keeping the addition rate of silver and halide salts close to the limit at which the generation of new grain nuclei occurs as described in JP-A-55-142329, the variation coefficient of the projected area of grains can be further reduced. .

Next, the tabular grains consisting essentially of silver bromide which serve as a base for depositing a silver salt having a higher solubility than silver bromide will be further described.

The tabular grains which form the basis of the present invention may have at least two layered structures having substantially different halogen compositions in the silver halide grain or may have a uniform composition.

Emulsions having a layered structure with different halogen compositions include those containing a high iodine layer in the core and a low iodine layer in the outermost layer, and those containing a low iodine layer in the core and a high iodine layer in the outermost layer. Good. Furthermore, the layered structure may consist of three or more layers.

The tabular emulsion which is the basis of the present invention can be prepared by the following precipitation method. The dispersion medium is placed in a commonly used reactor for producing a silver halide precipitate, which is equipped with a stirring mechanism.
Usually, the amount of dispersion medium introduced into the reactor in the first stage is at least about 10%, preferably 20-80%, of the amount of dispersion medium present in the emulsion in the final grain precipitation step. Water as the first dispersion medium to be placed in the reactor is water or a dispersion medium in a peptizer in water, and this dispersion medium may contain other components as necessary.
For example, one or more silver halide ripening agents and / or a metal doping agent described in detail later are blended. If the peptizer is initially present, its concentration should be at least 10% of the total peptizer present at the final stage of silver halide precipitation formation.
It is particularly preferably at least 20%. Add an additional dispersion medium into the reactor with the silver and halide salts,
It can be introduced from another jet. Generally, the proportion of dispersion medium is adjusted after completion of the halide salt introduction, especially in order to increase the proportion of peptizer.

Conventional bromide salts used to form silver halide grains.
Less than 10% by weight is initially present in the reactor to control the bromide ion concentration in the dispersion medium at the beginning of silver halide precipitation formation. Also, the dispersion medium in the reaction vessel initially does not substantially contain iodide ions. This is because the presence of iodo ions prior to the simultaneous addition of silver and bromide salts tends to produce thick nontabular grains.
Here, "substantially free of iodine ions" means that iodine ions are present in an amount insufficient to precipitate as another silver iodide phase as compared with bromide ions. The iodine concentration in the reactor before introducing the silver salt is preferably maintained at less than 0.5 mol% of the total halide ion concentration in the reactor. If the pBr of the dispersion medium is initially too high, the tabular silver iodobromide grains formed will be relatively thick and the grain thickness distribution will be broad. Also, the number of non-tabular grains increases. On the other hand, if pBr is too low, non-tabular grains are likely to be formed. As used herein, pBr is defined as the negative logarithm of the bromide ion concentration.

During the formation of the precipitate, silver, bromide and iodo salts are added to the reactor according to techniques well known for the formation of silver halide grains. Usually, an aqueous solution of a soluble silver salt such as silver nitrate is introduced into the reactor simultaneously with the introduction of the bromide and iodine salts. Also, the bromide and iodo salts are introduced as an aqueous salt solution, such as an aqueous solution of soluble ammonium, alkali metal (eg sodium or potassium) or alkaline earth metal (eg magnesium or calcium) halide salts. The silver salt is introduced into the reactor separately from the bromide salt and the iodo salt, at least initially.
The bromide salt and the iodine salt may be added separately or introduced as a mixture.

Introducing the silver salt into the reaction vessel initiates the grain nucleation step. Continued introduction of silver, bromide and iodide salts forms a population of silver bromide and grain nuclei that serve as precipitation sites for silver iodide. The grains enter a growth phase due to the precipitation of silver bromide and silver iodide on existing grain nuclei. The conditions for nucleation can be based on the method described in Japanese Patent Application No. 61-48950, but the method is not limited to this method, and for example, the nucleation temperature may be 5 to 55 ° C. it can.

The amount of gelatin in the reaction vessel during nucleation greatly affects the particle size distribution. As for gelatin concentration
It is preferably from 0.5 to 10% by weight, more preferably from 0.5 to 6% by weight.

The stirring speed and the shape of the reaction vessel also affect the particle size distribution.

As a stirring and mixing device, a device in which a reaction liquid as described in US Pat. No. 3,785,777 is added to the liquid and mixed is preferable, and the stirring rotation speed may not be too low or too high. When the stirring speed is low, the generation rate of non-parallel twin grains increases,
If it is too high, the frequency of generation of tabular grains decreases, and the size distribution also widens.

Further, it is most preferable that the bottom of the reaction container has a hemispherical shape.

A tabular grain of the present invention characterized in that a silver salt having a higher solubility than silver bromide is deposited on these base tabular grains, and then substantially silver bromide is deposited through a halogen conversion method. The average aspect ratio of is preferably 2 or more. It is more effective for the present invention that it is more preferably 3 or more, and further preferably 4 or more. The upper limit is preferably
It is 30 or less, more preferably 20 or less.

The average aspect ratio of tabular grains in the present invention is 0.1
For tabular grains having a grain diameter of μm or more, each is the average value of the grain diameter divided by the thickness. The thickness of the particles is measured by evaporating the metal from the oblique direction of the particles together with the latex for reference, measuring the shadow length on an electron micrograph, and calculating by referring to the shadow length of the latex. You can easily.

The particle diameter in the present invention is the diameter of a circle having an area equal to the projected area of the parallel outer surface of the particle.

The projected area of the particles can be obtained by measuring the area on an electron micrograph and correcting the photographing magnification.

The diameter of the tabular grains is preferably 0.15 to 5.0 µ. The thickness of tabular grains is 0.05 to 1.0μ
It is preferred that

The proportion occupied by tabular grains is preferably 30% or more, more preferably 50%, particularly preferably 80% or more of the total projected area.
% Or more.

When monodisperse tabular grains are used, more preferable results may be obtained. The structure and manufacturing method of monodisperse tabular grains are described in, for example, Japanese Patent Application No. 61-299155, but the shape thereof is briefly described. 70% or more of the total projected area of silver halide grains is the minimum. Occupied by tabular silver halide having a hexagonal shape in which the ratio of the length of the side having the maximum length to the length of the side having the length is 2 or less and having two parallel parallel surfaces as outer surfaces. Furthermore, the coefficient of variation of the grain size distribution of the hexagonal tabular silver halide grains (the variation of the grain size represented by the circle equivalent diameter of the projected area (standard deviation) divided by the average grain size) Has a monodispersity of 20% or less, an aspect ratio of 2.5 or more, and a particle size of 0.2 μm or more.

The grains of the present invention have a partially halogen-converted silver halochloride layer or silver citrate layer inside and have an aspect ratio of 2
The tabular silver bromide-based grains described above preferably have dislocations in the grain crystals.

Tabular grain dislocations are described, for example, in JF Hamilton, Phot.
Eng., 11 , 57, (1967) and T.Shiozawa, J.Soc.Phot.Sci.J
apan, 35 , 213, (1972) can be observed by a direct method using a transmission electron microscope at a low temperature. In other words, the silver halide grains taken out carefully so as not to apply pressure enough to cause dislocation to the grains from the emulsion are placed on a mesh for electron microscope observation, and the sample is placed so as to prevent damage (printout etc.) due to electron beams. Observation is carried out by the transmission method in the cooled state. At this time, the thicker the particles, the more difficult it is for an electron beam to pass. Therefore, a clearer image can be observed by using a high-pressure electron microscope (200 kV or more for particles having a thickness of 0.25 μm). From the photograph of the grains obtained by such a method, the position and number of dislocations of each grain when viewed from the direction perpendicular to the principal plane can be determined.

The dislocations of the tabular grains of the present invention exist in the major planes of the tabular grains. It is preferable for the present invention that dislocations are present over the entire main plane of the planar grain.

The tabular silver halide emulsion of the present invention may be made to coexist with cadmium salt, zinc salt, thallium salt, iridium salt or its complex salt, rhodium salt or its complex salt, iron salt or iron complex salt in the course of grain formation or physical ripening. Good.

During the production of the tabular grains of the present invention, a silver halide solvent may be used, if necessary, to control the grain size grain shape (diameter / thickness ratio, etc.), grain size distribution, and grain growth rate. The amount of solvent used depends on the reaction solution.
10 ^{-3 to} 1.0% by weight, particularly 10 ^-2 to 10 ^-1 % by weight is preferable.

For example, as the amount of solvent used increases, the particle size distribution can be made monodisperse and the growth rate can be increased. On the other hand, there is also a tendency that the particle thickness increases with the amount of solvent used.

Silver halide solvents often used include ammonia, thioethers and thioureas. For thioethers, US Pat.
No. 3, No. 3,790,387, No. 3,574,628, etc. can be referred to.

The silver halide emulsion of the present invention is usually subjected to spectral sensitization, but it is preferable to use it after spectral sensitization.

As the spectral sensitizing dye used in the present invention, usually a methine dye is used, which includes a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye,
Included are holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. To these dyes, any of the nuclei normally used for cyanine dyes as a basic heterocyclic nucleus can be applied. That is,
Pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus,
Imidazole nuclei, tetrazole nuclei, pyridine nuclei, etc .; nuclei in which alicyclic hydrocarbon rings are fused to these nuclei; and nuclei in which aromatic hydrocarbon rings are fused to these nuclei, that is, indolenine nuclei, benzindolenine nuclei , Indole nucleus, benzoxadol nucleus, naphthoxadol nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus,
Benzimidazole nucleus, quinoline nucleus, etc. can be applied.
These nuclei may be substituted on carbon atoms.

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, 2-thiooxazolidine-
A 5- or 6-membered heterocyclic nucleus such as 2,4-dione nucleus, thiazoline-2,4-dione nucleus, rhodanine nucleus or thiobarbituric acid nucleus can be applied.

Among the above dyes, the sensitizing dye particularly useful in the present invention is a cyanine dye. Specific examples of the cyanine dye useful in the present invention include a dye represented by the following general formula (I).

General formula (I) In the formula, Z ₁ and Z ₂ represent a heterocyclic nucleus usually used for a cyanine dye, particularly a thiazole nucleus, a thiazoline nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, an oxazole nucleus, an oxazoline nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, and a tetrazole nucleus. Represents a group of atoms necessary to complete a pyridine nucleus, quinoline nucleus, imidazoline nucleus, imidazole nucleus, benzimidazole nucleus, naphthoimidazole nucleus, selenazoline nucleus, selenazole nucleus, benzoselenazole nucleus, naphthoselenazole nucleus or indolenine nucleus. . These nuclei include a lower alkyl group such as a methyl group, a halogen atom, a phenyl group, a hydroxyl group, and a
To 4 alkoxy groups, carboxyl groups, alkoxycarbonyl groups, alkylsulfamoyl groups, alkylcarbamoyl groups, acetyl groups, acetoxy groups, cyano groups, trichloromethyl groups, trifluoromethyl groups, nitro groups, etc. Good.

L ₁ or L ₂ represents a methine group, a substituted methine group. Examples of the substituted methine group include a lower alkyl group such as a methyl group and an ethyl group, and a methine group substituted by a phenyl group, a substituted phenyl group, a methoxy group, an ethoxy group, and the like.

 R₁And R₂Is an alkyl group having 1 to 5 carbon atoms; carboxyl
Substituted alkyl group having a group; β-sulfoethyl group, γ-s
Rufopropyl group, δ-sulfobutyl group, 2- (3-sulfol group
Hoppropoxy) ethyl group, 2- [2- (3-sulfopro
(Poxy) ethoxy] ethyl group, 2-hydroxy sulfo
A substituted alkyl group having a sulfo group such as a propyl group;
N-substitution of allyl groups and other common cyanine dyes
It represents a substituted alkyl group used in the group. m₁Is 1,2
Or represents 3. X₁ Is iodine ion, bromine imine, p
-Flow of toluenesulfonic acid ion, perchlorate ion, etc.
Represents an acid anion group commonly used in cyanine dyes. n₁
Represents 1 or 2, and n has a betaine structure₁Is
It is 1.

Representative compounds of the particularly effective spectral sensitizing dyes used in the present invention are shown below.

Silver halide emulsions are usually chemically sensitized.

The most preferred embodiment of the emulsion of the present invention is chemical sensitization for use as a negative working silver halide emulsion. For chemical sensitization, for example, H. Frieser
Edited by Die Grundlagen der Photographischen Prozesse mit
Silberhalogeniden) (Academia Michel Ferragus Gezerschact 1968) pp. 675-734 can be used.

That is, a sulfur sensitization method using a compound containing a sulfur capable of reacting with active gelatin or silver (eg, thiosulfate, thioureas, mercapto compounds, rhodanines); a reducing substance (eg, stannous tin salt, Reduction sensitization using amines, hydrazine derivatives, formamidinesulfinic acid, silane compounds); using noble metal compounds (for example, gold complex salts and complex salts of Group VIII metals such as Pt, Ir, and Pd). A noble metal sensitization method or the like can be used alone or in combination.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, during storage or during photographic processing, or stabilizing photographic performance. Azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (particularly nitro- or halogen-substituted); heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, Mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines; the above heterocyclic mercapto compounds having a water-soluble group such as a carboxyl group or a sulfone group; a thioketo compound Azaindenes such as tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetraazaindenes); benzenethiosulfonic acids; Zensurufin acid; can be added to many compounds known as antifoggants or stabilizers, such as.

The timing of adding these antifoggants or stabilizers is usually
It is carried out after chemical sensitization, but more preferably, it can be selected during chemical ripening or before the start of chemical ripening. That is, in the silver halide emulsion grain formation process, during the addition of the silver salt solution, even after the addition until the start of chemical ripening, during the chemical ripening (during the chemical ripening time, preferably within 50% from the start, More preferably within 20% of the time).

Specific examples include a hydroxyazaindene compound, a benzotriazole compound, and a heterocyclic compound substituted with at least one mercapto group and having at least two aza nitrogen atoms in the molecule.

As the hydroxyazaindene compound, a compound represented by the following general formula (II) or (III) is preferable.

General formula (II) General formula (III) Here, R ₁ and R ₂ in the formula may be the same or different and each is a hydrogen atom; an aliphatic residue [alkyl group (for example, methyl group, ethyl group, propyl group, benzyl group, hexyl group, octyl group; Group, isopropyl group, sec-butyl group, t-butyl group, cyclohexyl group, cyclopentylmethyl group, 2-norbornyl group, etc .; alkyl group substituted with an aromatic residue (for example, benzyl group, phenethyl group, benzhydryl group, 1-naphthylmethyl group, 3-phenylbutyl group, etc.); alkyl group substituted with an alkoxy group (eg, methoxymethyl group, 2-methoxyethyl group, 3-ethoxypropyl group, 4-methoxybutyl group, etc.); hydroxy group , An alkyl group substituted with a carbonyl group or an alkoxycarbonyl group (for example, a hydroxymethyl group, 2-hydroxy group). Rokishimechiru group, 3-hydroxybutyl group, carboxymethyl group, 2-carboxyethyl group, 2- (such as methoxycarbonyl) ethyl] or an aromatic residue [aryl group (e.g. phenyl, 1
An aryl group having a substituent (for example, p-tolyl group, m-ethylphenyl group, m-cumenyl group, mesityl group, 2,3-xylyl group, p-chlorophenyl group, o-bromophenyl group, p-hydroxyphenyl group, 1-hydroxy-2-naphthyl group, m-methoxyphenyl group, p-ethoxyphenyl group, p-carboxyphenyl group, o- (methoxycarbonyl) phenyl group, m
-(Ethoxycarbonyl) phenyl group, 4-carboxy-1-naphthyl group, etc.].

Further, the total carbon number of R ₁ and R ₂ is preferably 12 or less.

 n represents 1 or 2.

Specific examples of the hydroxytetraazaindene compound represented by the general formula (II) or (III) are shown below. However,
The compounds used in the method of the present invention are not limited only to these.

II-1 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene II-2 4-hydroxy-1,3,3a, 7-tetraazaindene II-3 4-hydroxy-6-methyl -1,2,3a, 7-Tetraazaindene II-4 4-hydroxy-6-phenyl-1,3,3a, 7-tetraazaindene II-5 4-Methyl-6-hydroxy-1,3,3a , 7-Tetraazaindene II-6 2,6-Dimethyl-4-hydroxy-1,3,3a, 7-
Tetraazaindene II-7 4-hydroxy-5-ethyl-6-methyl-1,
3,3a, 7-Tetraazaindene II-8 2,6-dimethyl-4-hydroxy-5-ethyl-1,3,3a, 7-tetraazaindene II-9 4-hydroxy-5,6-dimethyl- 1,3,3a, 7−
Tetraazaindene II-10 2,5,6-trimethyl-4-hydroxy-1,3,3a
-7-Tetraazaindene II-11 2-methyl-4-hydroxy-6-phenyl-
1,3,3a, 7-Tetraazaindene II-12 4-hydroxy-6-ethyl-1,2,3a, 7-tetraazaindene II-13 4-hydroxy-6-phenyl-1,2,3a, 7-Tetraazaindene II-14 4-Hydroxy-1,2,3a, 7-tetraazaindene II-15 4-Methyl-6-hydroxy-1,2-7-tetraazaindene II-16 5,6- Trimethylene-4-hydroxy-1,3,3a,
7-Tetraazaindene Examples of the benzotriazole compound include those represented by the following general formula IV.

(General formula IV) Wherein p is 0 and an integer from 1 to 4. R ₃ is
A halogen atom (chlorine, bromine or iodine atom) or an aliphatic group (including a saturated aliphatic group and an unsaturated aliphatic group), for example, an unsubstituted alkyl group preferably having 1 to 8 carbon atoms (for example, a methyl group, ethyl Group, n-propyl group, hexyl group, etc.); substituted alkyl group (preferably an alkyl radical having 1 to 4 carbon atoms, for example,
Vinylmethyl group, aralkyl group (eg, benzyl group, phenethyl group, etc.), hydroxyalkyl group (eg, 2-
Hydroxyethyl group, 3-hydroxypropyl group, 4-
An hydroxy group, an acetoxyalkyl group (eg, a 2-acetoxyethyl group, a 3-acetoxypropyl group), an alkoxyalkyl group (eg, a 2-methoxyethyl group, a 4-methoxybutyl group), or an aryl group (eg, A phenyl group). R ₃ is more preferably a halogen atom (chlorine or iodine atom)
Alternatively, it is an alkyl group having 1 to 3 carbon atoms (methyl group, ethyl group, or propyl group).

Next, a heterocyclic compound substituted with at least one mercapto group and having at least two aza nitrogen atoms in the molecule (hereinafter, a nitrogen-containing heterocyclic compound having a mercapto group) will be described. The heterocycle of such a compound may have a heteroatom such as an oxygen atom, a sulfur atom or a selenium atom in addition to the nitrogen atom. Preferred compounds are monocyclic heterocyclic compounds having at least two 5- or 6-membered aza nitrogen atoms, or two rings formed by condensing two or three heterocycles having at least one aza nitrogen atom, or A tricyclic heterocyclic compound in which a mercapto group is substituted on the carbon atom adjacent to the aza nitrogen.

In the nitrogen-containing heterocyclic compound having a mercapto group used in the present invention, a pyrazole ring as a heterocycle, 1,2,4
-Triazole ring, 1,2,3-triazole ring, 1,3,4-thiadiazole ring, 1,2,3-thiadiazole ring, 1,2,4-thiadiazole ring, 1,2,5-thiadiazole ring, 1 , 2,3,4-
A tetrazole ring, a pyridazine ring, a 1,2,3-triazine ring, a 1,2,4-triazine ring, a 1,3,5-triazine ring, a ring in which two to three of these rings are condensed, for example, a triazolotriazole ring , Diazaindene ring, triazaindene ring,
A tetrazaindene ring, a pentazaindene ring or the like can be applied. A heterocycle in which a monocyclic heterocycle and an aromatic ring are condensed, such as a phthalazine ring and an indazole ring, can also be applied.

Among these rings, preferred are 1,2,4-triazole ring, 1,3,4-thiadiazole ring, 1,2,3,4-tetrazole ring, 1,2,4-triazine ring and triazolotriazole And a tetrazaindene ring.

Specific examples of the nitrogen-containing heterocyclic compound having a mercapto group used in the present invention are listed below.

(However, it is not limited to these.) The above II, III, IV and V used in the present invention
The addition amount of the compound (A) cannot be uniquely determined by the addition method or the amount of silver halide, but is preferably 10 ^-7 mol to 10 ^-2 mol, more preferably 10 ^-5 to 10 mol per mol of silver halide. ^-2 moles.

The silver halide photographic emulsion of the present invention comprises a cyan coupler,
Color couplers such as magenta couplers and yellow couplers and compounds that disperse couplers can be included.

A specific example is Research Disclosure (RD) N.
No. 17643, VII-C-G.

As the yellow coupler, for example, U.S. Pat.
No. 501, No. 4,022,620, No. 4,326,024, No. 4,40
No. 1,752, JP-B-58-10739, UK Patent No. 1,425,020,
No. 1,476,760 and the like are preferable.

As the magenta coupler, 5-pyrazolone-based and pyrazoloazole-based compounds are preferable, and US Patent No. 4,310,
Nos. 619 and 4,351,897, European Patent No. 73,636, U.S. Patent Nos. 3,061,432 and 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-33552
Issue, Research Disclosure No. 24230 (June 1984
JP-A-60-43659, U.S. Pat. Nos. 4,500,630 and 4,540,654 are particularly preferable.

Examples of cyan couplers include phenol-based and naphthol-based couplers, and U.S. Pat.Nos. 4,052,212, 4,146,396, 4,228,233, and 4,296,200.
No. 2,369,929, No. 2,801,171, No. 2,772, 162, No. 2,895,826, No. 3,772,002, No. 3,758,308,
No. 4,334,011, No. 4,327,173, West German Patent Publication No. 3,
No. 329,729, European Patent No. 121,365A, U.S. Patent No. 3,446,6
No. 22, No. 4,333,999, No. 4,451,559, No. 4,427,
No. 767, EP 161,626A and the like are preferred.

Colored couplers to correct unwanted absorption of colored dyes are VII of Research Disclosure No. 17643.
-G section, U.S. Pat. No. 4,163,670, Japanese Patent Publication No. 47-39413,
U.S. Patents 4,004,929, 4,138,258, British Patent 1,
Those described in No. 146,368 are preferable.

As a coupler in which the coloring dye has an appropriate diffusibility,
Those described in U.S. Pat. No. 4,366,237, British Patent No. 2,125,570, European Patent No. 96,570 and West German Patent (Publication) No. 3,234,533 are preferable.

Typical examples of polymerized dye-forming couplers are U.S. Pat.Nos. 3,451,820, 4,080,211 and 4,367,282.
No. 2,102,173 and the like.

A coupler which releases a photographically useful residue upon coupling may be used at the same time. DIR couplers that release development inhibitors are RD17643, patents described in the paragraph VII-F, JP-A-57-151944, 57-154234 and 60-184248.
And those described in U.S. Pat. No. 4,248,962 are preferred.

Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent Nos. 2,097,140 and 2,1.
Those described in 31,188, JP-A-59-157638 and JP-A-59-170840 are preferable.

Other couplers that can be used in a light-sensitive material using the silver halide photographic emulsion of the present invention include competitive couplers described in U.S. Pat.No. 4,130,427, U.S. Pat.
Examples include multi-equivalent couplers described in 83,472, 4,338,393, 4,310,618 and the like, and couplers releasing a dye that recovers color after separation described in EP 173,302A.

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

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

The steps of the latex dispersion method, effects, and specific examples of latex for impregnation are described in US Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

Suitable supports that can be used in the silver halide photographic emulsion of the present invention are described, for example, in RD. No. 17643, page 28, and RD. No. 1871.
6, page 647, right column to page 648, left column.

Various other additives can be used in the silver halide emulsion used in the present invention. That is, a surfactant, a hardener, a thickener, a dye, an ultraviolet absorber, an antistatic agent, a whitening agent, a desensitizer, a developer, an anti-fading agent, a mordant and the like can be used.

About these additives, Research Disclosure magazine (RESEARCH DISCLOSURE, RD-17643), vol.17
6, pages 22-31 (Ducember, 1978), "The Theory of the Photographic Process 4th Edition" (THE
THEORY OF THE PHOTOGRAPHIC PROCESS, 4thEd.) TH James Edition (1977, Macmillan Publishing Co.In
c.) etc.

The binder used in the silver halide emulsion to which the present invention is applied is preferably gelatin (lime-processed gelatin, acid-processed gelatin, etc.), but in addition to gelatin, derivative gelatin such as phthalated gelatin, cellulose derivative,
Polyvinyl acetate, polyacrylamide, polyvinyl alcohol, etc. are used.

The silver halide photographic light-sensitive material which can be used in the present invention includes a color positive film, a color paper, a color negative film, a color reversal film (which may or may not contain a coupler), a plate-making photographic light-sensitive material and a cathode ray tube. Examples of photosensitive materials for displays (eg, emulsion X-ray recording photosensitive materials, direct and indirect imaging materials using screens), silver salt diffusion transfer process (Silver Salt diffusion)
transfer process) light-sensitive material, color diffusion transfer process light-sensitive material, heat-development light-sensitive material, and the like.

Color photographic light-sensitive materials using the silver halide photographic emulsion of the present invention are described in RD. No. 17643, pp. 28-29, and RD.
651 in the left column to the right column.

The color developer used for the development processing of the light-sensitive material of the present invention,
An alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component is preferred. Aminophenol compounds are also useful as the color developing agent, but p-
Phenyldiamine compounds are preferably used, and representative examples thereof include 3-methyl-4-amino-N, N-diethylaniline and 3-methyl-4-amino-N-ethyl-.
N-β-hydroxyethylaniline, 3-methyl-4-
Amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-
N-β-methoxyethylaniline and sulfates thereof,
Hydrochloride or p-toluene sulfonate may be mentioned. Two or more of these compounds can be used in combination depending on the purpose.

Color developing solutions include alkali metal carbonates, pH buffers such as borates or phosphates, bromide salts, iodide salts,
It is common to include a development inhibitor such as benzimidazoles, benzothiazoles or mercapto compounds, or an antifoggant. If necessary, hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenylsemicarbazides, triethanolamine, catecholsulfonic acids, triethylenediamine (1,4-diazabicyclo [2,2,2] octane) Various preservatives, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye forming couplers, competitive couplers, fogging agents such as sodium boron hydride. , Chelating agents such as auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting agents, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids, for example, ethylene. Diamine tetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexane diamine tetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene--1,
1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof It can be raised as a representative example.

When the reversal process is performed, black and white development is usually performed before color development. This black and white developer contains dihydroxybenzenes such as hydroquinone, 1-phenyl-3-
Known black-and-white developing agents such as 3-pyrazolidones such as pyrazolidone or aminophenols such as N-methyl-p-aminophenol can be used alone or in combination.

The color developing solution and the black and white developing solution generally have a pH of 9 to 12. The replenishment amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per 1 square meter of light-sensitive material, and is 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air. Further, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developing solution.

The photographic emulsion tank after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further processing with two continuous bleach-fix baths,
The fixing treatment before the bleach-fixing treatment or the bleaching treatment after the bleach-fixing treatment can be optionally carried out according to the purpose.
Examples of bleaching agents include iron (III), cobalt (III),
Compounds of polyvalent metals such as chromium (VI) and copper (II), peracids, quinones, nitro compounds and the like are used. Typical bleaching agents are ferricyanide; dichromate; iron (II
I) or cobalt (III) organic complex salts such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3
-Aminopolycarboxylic acids such as diaminopropane tetraacetic acid and glycol ether diamine tetraacetic acid or complex salts such as citric acid, tartaric acid and malic acid; persulfates; bromates; permanganates; nitrobenzenes and the like can be used. it can. Of these, aminopolycarboxylic acid iron (II) including ethylenediaminetetraacetic acid iron (III) complex salts
I) Complex salts and persulfates are preferable from the viewpoint of rapid processing and prevention of environmental pollution. Furthermore, iron (III) aminopolycarboxylate
Complex salts are particularly useful in both bleaching solutions and bleach-fixing solutions. The pH of the bleaching solution or the bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 5.5 to 8, but the processing can be carried out at a lower pH in order to speed up the processing.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath. Specific examples of useful bleaching accelerators are described in the following specifications: US Pat. No. 3,893,858, West German Patent 1,290,812, JP-A-53-9.
5,630, Research Disclosure No. 17,129 (July 1978), etc., compounds having a mercapto group or a disulfide bond; thiazolidine derivatives described in JP-A No. 50-140,129; US Pat. No. 3,706,561. Thiourea derivatives; iodide salts described in JP-A-58-16,235; polyoxyethylene compounds described in West German Patent 2,748,430; polyamine compounds described in JP-B-45-8836; bromide ion and the like can be used. Among them, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large accelerating effect, and the compounds described in US Pat. No. 3,893,858, West Patent No. 1,290,812 and JP-A-53-95,630 are particularly preferable. Further, the compounds described in US Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography.

Examples of the fixing agent include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodide salts, but thiosulfates are generally used.
In particular, ammonium thiosulfate can be used most widely. As a preservative for the bleach-fix solution, sulfite, bisulfite or carbonyl bisulfite adduct is preferable.

The silver halide color photographic light-sensitive material of the present invention generally undergoes a washing and / or stabilizing step after desilvering. The amount of rinsing water in the rinsing step depends on the characteristics of the light-sensitive material (for example, depending on the material used such as a coupler), the purpose, and the rinsing water temperature.
It can be set in a wide range depending on the number of washing tanks (the number of stages), a replenishment system such as countercurrent and forward flow, and various other conditions. Of these, the relationship between the number of washing tanks and the water volume in the multi-stage countercurrent system is described in the Journal of the Society of Motion Picture and T
It can be determined by the method described in elevision Engineers Volume 64, P.248-253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problem arises. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method of reducing calcium ion and magnesium ion described in Japanese Patent Application No. 61-131632 can be very effectively used. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8,542, chlorine-based bactericides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., Hiroshi Horiguchi "Chemistry of antifungal agents" The sterilizing agents described in "Microbial Sterilization, Sterilization, and Antifungal Technologies" edited by the Society of Hygiene Technology and "Encyclopedia of Antibacterial and Antifungal Agents" edited by Japan Society for Antibacterial and Antifungal Agents can also be used.

The pH of washing water in the processing of the light-sensitive material of the present invention is 4-
9, preferably 5-8. The washing water temperature and washing time can be variously set depending on the characteristics of the light-sensitive material, application, etc., but in general, at 15-45 ° C for 20 seconds-10 minutes, preferably at 25-40 ° C.
A range of 30 seconds-5 minutes is selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such a stabilizing process, the method disclosed in
Known methods described in 57-8,543, 58-14,834, and 60-220,345 can all be used.

Further, there is a case where a stabilizing treatment is further performed after the water washing treatment, and an example thereof is a stabilizing bath containing formalin and a surfactant, which is used as a final bath of a color light-sensitive material for photographing. . Various chelating agents and fungicides can also be added to this stabilizing bath.

The overflow solution accompanying the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up the processing.
For incorporation, it is preferable to use various precursors of color developing agents. For example, indaniline compounds described in U.S. Pat. Examples thereof include salt complexes and urethane compounds described in JP-A-53-135,628.

The silver halide color light-sensitive material of the present invention contains various 1-phenyl-containing compounds, if necessary, for the purpose of promoting color development.
You may incorporate 3-pyrazolidones. Typical compounds are JP-A-56-64,339, JP-A-57-14,4547, and JP-A-58-11.
No. 5,438 is described.

The various treatment liquids in the present invention are used at 10 ° C to 50 ° C. Normally, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature accelerates the processing to shorten the processing time, and a lower temperature lowers the image quality to improve the stability of the processing liquid. be able to. Further, in order to save silver in the light-sensitive material, processing using cobalt intensification or hydrogen peroxide intensification described in West German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be performed.

(Examples) Examples will be described below, but the present invention is not limited to these examples.

Example-1 The characteristics of the emulsion of the present invention will be described.

970 ml of an aqueous solution containing 32 g of gelatin and 3 g of KBr was kept at 40 ° C., and an aqueous solution of silver nitrate (AgNO ₃ , 32.7 g) and an aqueous solution of halogen (KBr23.8 g, KI 2.8 g) were added over 4 minutes under constant stirring. . After raising the temperature of the solution to 75 ℃, KBr7g and NaC
l6g was added and aged for 32 minutes. At this time, the silver potential of the reaction solution was -60 mV with respect to the saturated calomel electrode. Then, an aqueous solution of silver nitrate was added until the silver potential of the reaction solution reached +150 mV. Thereafter, an aqueous silver nitrate solution and an aqueous halogen solution (containing 11.7% by weight of KI with respect to KBr) were added over 4.6 minutes to bring the silver potential of the reaction solution to +20 mV. The amount of silver nitrate used was 50.3 g. After this, an aqueous solution of silver nitrate (AgNO ₃
91.5g) and halogen aqueous solution (KI is 9.0% by weight with respect to KBr)
(Including) was added over 21 minutes. At this time, the silver potential of the reaction solution was kept at +20 mV with respect to the saturated calomel electrode. This emulsion was desalted, gelatin and water were added, and pH 6.9 and pAg8.
It was adjusted to 3 and designated as Em-A.

Em-A has an average thickness of 0.25 μm, an average circle equivalent diameter of 0.77 μm,
It was an average grain emulsion having an average aspect ratio of 3.43. Em−
The silver chloride content of A was 5.5 mol% as measured by the EPMA method. It was found that 40% of the subsequently deposited silver chloride was converted to halogen. The dislocations of the particles of the present invention were directly observed using a transmission electron microscope described in the text. As an electron microscope, JEM-2000FX manufactured by JEOL Ltd. was used, and observation was performed at a voltage of 200 KV and at a liquid nitrogen temperature. The results are shown in Fig. 1. Dislocation lines were innumerable on the principal planes of tabular grains.

Next, the effect on the pressure property and sensitivity of the grain of the present invention in which a specific position inside the tabular grain is selectively halogen-converted will be described.

In the manufacturing method of Em-A, after raising the temperature of the solution to 75 ° C., 7 g of KBr was added and aged for 32 minutes. That is, no NaCl was added. At this time, the silver potential of the reaction solution was -60 mV with respect to the saturated calomel electrode. Then, an aqueous solution of silver nitrate was added until the silver potential of the reaction solution reached +20 mV. After this, silver nitrate solution and halogen solution (KI for KBr
Of 11.7% by weight) was added while maintaining the silver potential of the reaction solution at +20 mV. The amount of silver nitrate used was 50.3 g.

After this, an aqueous solution of silver nitrate (91.5 g of AgNO ₃ ) and an aqueous solution of halogen (containing 9.0% by weight of KI with respect to KBr) were added over 21 minutes. At this time, the silver potential of the reaction solution was kept at +20 mV with respect to the saturated calomel electrode. This emulsion was desalted, and gelatin and water were added to adjust the pH to 6.9 and pAg to 8.3 at 40 ° C to obtain Em-B.

Em-B was a tabular grain having a thickness of 0.23 µm, an equivalent circle diameter of 0.80 µm and an aspect ratio of 3.56. The grains do not contain silver chloride. Further, the results of similarly observing the particles with a low temperature transmission electron microscope are shown in FIG. There are no dislocation lines.

Dye I-1 was added to Em-A and Em-B at 0.
After adding 98 × 10 ^-3 mol, optimum chemical sensitization was performed with sodium thiosulfate, potassium chloroaurate, and potassium thiocyanate at 64 ° C., respectively.

Next, a coating aid and a hardening agent were added and the mixture was coated on a cellulose triacetate film base so that Ag was 2 g / m ² .

The pressure characteristics were evaluated as follows. 40% relative humidity
The coated sample was fixed at one end with the emulsion surface inside, and was bent along a stainless pipe having a diameter of 10 mm while rotating 180 ° at a bending speed of 360 ° / sec. These folds were done 10 seconds before or 10 seconds after exposure.

The coating emulsion was exposed to a tungsten bulb (color temperature 2854K) through a continuous wedge for 1 second. The exposed coating emulsion was prepared by using the following surface developer (MAA-1) at 20 ° C.
Developed for minutes.

Metol 2.5 g d-Ascorbic acid 10.0 g Potassium bromide 1.0 g Nabox 35.0 g Water 1000 ml The sensitivity and fog of the emulsion obtained were evaluated in the bent portion and the non-folded portion. The sensitivity was indicated by the relative value of the reciprocal of the exposure amount required for the optical density to become fogging plus 0.1.

 The results thus obtained are shown in Table 1.

As is apparent from Table 1, the emulsion of the present invention in which silver chloride was selectively halogen-changed only in a limited area inside the tabular grains had a significantly small increase in fog due to pressure. The sensitivity was high and the gradation was hard.

Example-2 Particles having a partially halogen-modified silver chloride layer inside the grain of the present invention have a higher pressure than conventional grains having a high iodine layer deposited therein or grains having a high iodine layer provided by conversion. The superiority and the sensitivity will be described.

Gelatin 30g, potassium bromide 10.3g, 0.5wt in water 1
% Thioether _{(HO (CH 2) 2 S} (CH 2) 2 S (CH 2) 2 OH) aqueous solution of 20cc
In a container maintained at 73 ° C (pAg 9.0, pH 6.5) with stirring, aqueous silver nitrate solution (AgNO ₃ 4.5g) and halogen aqueous solution (KBr 3.15g KI 0.088g, HO (CH ₂ ) ₂ S (CH ₂ ) ₂ S (CH ₂ ) ₂ OH5wt
% 0.4% aqueous solution. ) Was added simultaneously for 10 seconds, and then an aqueous silver nitrate solution (AgNO ₃ 95.5 g) and an aqueous halogen solution (K
Br 69.6gKI 1.865g, HO and _{(CH 2) 2 S (CH} 2) 2 S (CH 2) 2 OH5wt% aqueous solution containing 9.6Cc. ) Was added simultaneously by the double jet method over 65 minutes. The obtained silver halide grains had an average diameter of 1.90 μm and an aspect ratio of 9.9. The silver halide grains were chemically sensitized with chloroaurate and sodium thiosulfate, and then a coating aid and an antifoggant were added.
This emulsion was designated as Em-C.

KI was removed from the second stage halogen aqueous solution, which is almost the same as Em-C, but the first stage. Then, 5 minutes after starting the simultaneous addition of the second-stage silver nitrate aqueous solution and the halogen aqueous solution by the double jet method, the KI aqueous solution (KI 1.953
g) was added by the triple jet method over 10 minutes. The tabular grains obtained had an average diameter of 1.85 μm and an aspect ratio of 10.8. Chemical sensitization similar to Em-C
D.

Although approximately the same as Em-D, the addition of the second stage silver nitrate aqueous solution and the halogen aqueous solution was simultaneously stopped by the double jet method, and 20 minutes after the addition was temporarily stopped, 4.88 cc of 10% KI aqueous solution was added. The obtained particles have an average diameter of 1.73μ.
It was m and the aspect ratio was 10.1. Chemical sensitization was performed in the same manner as Em-D to obtain Em-E.

Although it is almost the same as Em-C, the addition of the silver nitrate aqueous solution and the halogen aqueous solution in the first step was stopped by the double jet method at the same time 40 minutes after the addition was temporarily stopped, and 5 g of NaCl was added.
Was added. After that, only the silver nitrate aqueous solution was added to adjust the silver potential to 100 mV with respect to the saturated calomel electrode. A halogen aqueous solution was added to restore the silver potential to sensitize for 5 minutes, and then the silver nitrate aqueous solution and the halogen aqueous solution were continuously added.
The obtained particles had an average diameter of 1.60 μm and an aspect ratio of 8.9. Chemical sensitization was performed in the same manner as Em-C to obtain Em-F.

Em-C, D, E, and F were coated on one surface of a polyethylene terephthalate film having an undercoating agent of 180 μm at the same time as the surface protective layer so that the coated silver amount was 2.5 g / m ² . The method of treating the coating liquid for the surface protective layer was as follows.

A 10% aqueous gelatin solution consisting of gelatin, sodium polystyrene sulfonate, fine particles of polymethylmethacrylate (average particle size 3.0 μ), saponin and 2,4-dichloro-6-hydroxy-s-triazine.

 The pressure characteristics were evaluated in the same manner as in Example-1.

The exposed coating emulsion was developed with the following developer at 35 ° C. for 25 seconds.

 1-Phenyl-3-pyrazolidone 1.5g Hydroquinone 30g 5-Nitroindazole 0.25g KBr 3.7g Anhydrous sodium sulfite 50g Potassium hydroxide 20g Boric acid 10g 25% Glutaraldehyde aqueous solution 20ml Add water to bring the total volume to 1.

(The pH was adjusted to 10.20.) The results thus obtained are shown in Table 2.

As is clear from Table-2, the grains having a silver chloride layer partially halogen-modified inside the grains are conventional emulsions having improved pressure characteristics, that is, grains having a high iodine layer inside the grains, or grains inside the grains. It was significantly more sensitive than iodine-converted particles, yet had improved pressure characteristics.

Example 3 It will be described that the present invention is effective also for a double structure particle in which the inside of the particle has a higher iodine than the surface.

970 ml of an aqueous solution containing 32 g of gelatin and 3 g of KBr was kept at 40 ° C., and an aqueous silver nitrate solution (AgNO ₃ 32.7 g) and an aqueous halogen solution (KBr 23.8 g, KI 2.8 g) were added over 4 minutes under constant stirring. After raising the temperature of the solution to 75 ° C., 7 g of KBr was added and the mixture was aged for 32 minutes. After that, an aqueous solution of silver nitrate (AgNO
₃ 71.4g) and halogen aqueous solution (KI to KBr 42% by weight)
(Including) was added over 33.9 minutes. At this time, the silver potential of the reaction solution was kept at +20 mV with respect to the saturated calomel electrode.
Then, an aqueous silver nitrate solution (AgNO ₃ 70.4 g) and an aqueous KBr solution were added over 16 minutes while keeping the silver potential at +20 mV with respect to the saturated calomel electrode. The obtained particles have an average equivalent circle diameter of 0.80μ
The average grain emulsion had an average particle size of m, an average thickness of 0.23 μm and an average aspect ratio of 3.6. An X-ray diffraction measurement of the emulsion particles by a powder method showed double peaks, and it was clearly a double structure particle having a high iodine inside the grain and a low iodine surface. This emulsion was designated as Em-G.

In the manufacturing method of Em-G, 3 g of NaCl was added after the addition of the second stage silver nitrate was completed. Thereafter, an aqueous silver nitrate solution was added to make the silver potential of the reaction solution +150 mV. After the KBr aqueous solution was added to adjust the silver potential to +20 mV and aging was performed for 3 minutes, the silver nitrate aqueous solution and the KBr aqueous solution were added. At this time, the silver potential was kept at +20 mV. 70.4 g of AgNO ₃ was used in this process. The obtained particles have a circle equivalent diameter of 0.80 μm, a thickness of 0.23 μm, and an aspect ratio.
It was a tabular grain of 3.6. This emulsion was designated as Em-H.

Em-G and Em-H were desalted and gelatin and water were added to adjust pH 6.8 and pAg 8.3 at 40 ° C.
After adding 0.98 × 10 ^-3 mol to mol, 1.4 × 10 ^-4 mol to compound V-8 was added to 1 mol of silver, and sodium thiosulfate, potassium chloroaurate, and potassium thiocyanate were optimally used. Chemically sensitized.

The cellulose triacetate film support provided with an undercoat layer was coated with the emulsions of Em-G and H and the protective layer at the coating amounts shown in Table 3.

Table 3 Emulsion coating conditions (1) Emulsion layer Emulsion ... Em-G or H (silver 2.1 × 10 ⁻² mol / m ² ) Coupler (1.5 × 10 ⁻³ mol / m ² ) Tricresyl phosphate (1.10 g / m ² ) Gelatin (2.30 g / m ² ) (2) Protective layer 2,4-dichlorotriazine-6-hydroxy-s-triazine sodium salt (0.08 g / m ² ) Gelatin ( 1.80g / m ² ) After leaving these samples under conditions of 40 ° C and 70% relative humidity for 14 hours, they were exposed for 1/100 seconds through a continuous wedge,
The following color development processing was performed.

 The density of the treated sample was measured with a green filter.

 The developing treatment used here was carried out at 38 ° C. under the following conditions.

1. Color development …… 2 minutes 45 seconds 2. Bleaching …… 6 minutes 30 seconds 3.Washing …… 3 minutes 15 seconds 4. Settling …… 6 minutes 30 seconds 5. Washing …… 3 minutes 15 seconds 6. Stability: 3 minutes 15 seconds The composition of the processing liquid used in each process is as follows.

Color developer Sodium nitrilotriacetate 1.0g Sodium sulfite 4.0g Sodium carbonate 30.0g Potassium bromide 1.4g Hydroxylamine sulfate 2.4g 4- (N-ethyl-N-β hydroxyethylamino)
2-Methyl-aniline sulfate 4.5 g Water added 1 Bleach Ammonium bromide 160.0 g Ammonia water (28%) 25.0 ml Ethylenediamine-tetraacetic acid sodium iron salt 130 g Glacial acetic acid 14 ml Water added 1 Fixer Tetrapolyline Sodium acid salt 2.0 g Sodium sulfite 4.0 g Ammonium thiosulfate (70%) 175.0 ml Sodium bisulfite 4.6 g Water was added 1 Stabilized solution Formalin 8.0 ml Water was added 1 Pressure characteristics were evaluated in the same manner as in Example-1. It was

The sensitivity was expressed as the reciprocal of the exposure amount displayed in lux · second at a density of 0.2 on the fog.

The results thus obtained are shown in Table 4 together with the characteristics of the emulsion.

As is clear from Table 4, tabular grains having a partially halogen-converted silver chloride layer inside the grain of the present invention have a pressure higher than that of a double structure grain in which the inside of the grain has higher iodine than the surface. It has excellent properties and higher sensitivity.

 In addition, the graininess of these samples was evaluated.

The RMS granularity is described in "The Theory of the Photographic Process", page 619, published by Macmillan Co., Ltd., after uniformly exposing the sample to a light amount giving a density of 0.2 on the fog and performing the development processing described above. It measured using the G filter by the method mentioned above.

The gamma value was expressed by the reciprocal of the difference between the exposure amount giving a density of 1.0 and the exposure amount giving a density on sensitometry. The obtained results are shown in Table-5.

Table 5 shows that the emulsion of the present invention has a hard gradation and an excellent granularity.

Example-4 The effect of the deposition mole number of the silver chloride layer inside the tabular grain of the present invention on the pressure property will be described.

An aqueous solution containing gelatin and KBr was kept at 40 ° C., and an aqueous silver nitrate solution (AgNO ₃ , 32.7 g) and an aqueous halogen solution (KBr, 24.9 g, KI, 1.3 g) were added over 4 minutes under constant stirring. After adding an aqueous solution containing KBr and gelatin, the temperature was raised to 70 ° C. and aging was performed for 30 minutes. At this time, the silver potential of the reaction solution was -50 mV with respect to the saturated calomel electrode. The silver potential was adjusted to +70 mV by adding an aqueous silver nitrate solution. This emulsion is Em-I
And

An aqueous solution of silver nitrate and an aqueous solution of sodium chloride were added to Em-I by a double jet, and the amount of each was 0.
2 mol, 4 mol, 8 mol, 16 mol, 32 mol and 64 mol of silver chloride were deposited. Then, the halogen solution (K for KBr
(Containing 5.3 wt% of I), the silver potential of the reaction solution is set to 0 mV, and 5
Aged for minutes. Then, add silver nitrate aqueous solution and halogen aqueous solution (containing 5.3% by weight of KI to KBr) with the addition amount of silver nitrate.
Added at 4.74 g / min. At this time, the silver potential of the reaction solution was kept at 0 mV with respect to the saturated calomel electrode. The amount of silver nitrate added after the formation of Em-I was kept constant at 152.3 g. Silver chloride was deposited at 0, 2mol, 4mol, 8mol, and 16mol, respectively.
-J, Em-K, Em-L, Em-M, and Em-N. These emulsions were desalted, gelatin and water were added, and the pH was adjusted to 6.
9, adjusted to pAg 7.5. Dye I-14 is 1.4 for 1 mol of silver
After adding × 10 ^-3 mol, optimum chemical sensitization was performed with sodium thiosulfate, potassium chloroaurate and sodium thiocyanate at 64 ° C.

 The same coating as in Example-3 was performed.

After leaving these samples under the conditions of 40 ° C and 70% relative humidity for 14 hours, BPN42 filter (Fuji Photo Film Co., Ltd. gelatin filter) is used for intrinsic sensitivity, and color sensitization sensitivity is used for viewing. Through SC52 filter (Fuji Photo Film Co., Ltd. gelatin filter) and continuous wedge
After exposure for 1/100 seconds, the same color development processing as in Example-3 was performed.

 The density of the treated sample was measured with a green filter.

The evaluation of the pressure characteristics was performed by the same method as in Example-1.

 The obtained results are shown in Table-6.

Em-K, L, and M according to the present invention had significantly improved pressure resistance. However, Em- with 16 mol of silver chloride layer deposited
The grain thickness of N increased and the aspect ratio became 1.9.
In addition, it was also confirmed in another experiment that the particles became spherical when the number of moles of AgCl deposited was further increased compared to Em-N.

Example 5 The effect of the position of the partially halogen-converted silver chloride layer of the present invention inside the tabular grains on the pressure property will be described.

An aqueous solution containing gelatin and KBr was kept at 40 ° C., and an aqueous silver nitrate solution (AgNO ₃ , 32.7 g) and an aqueous halogen solution (KBr, 24.9 g, KI, 1.3 g) were added over 4 minutes under constant stirring. After adding an aqueous solution containing KBr and gelatin, the temperature was raised to 70 ° C. and aging was performed for 30 minutes. The silver potential of the reaction solution was -50 mV against the saturated calomel electrode. The silver potential was adjusted to +0 mV by adding an aqueous silver nitrate solution. This emulsion was designated as Em-Q. An aqueous solution of silver nitrate and an aqueous solution of halogen (containing 5.3% by weight of KI relative to KBr) were added to Em-Q at an amount of silver nitrate of 4.74 g / min. At this time, the silver potential of the reaction solution was kept at 0 mV with respect to the saturated calomel electrode. At this time, 152.3 g of silver nitrate was used. This emulsion was designated as Em-R.

10 g of NaCl was added to Em-Q, and an aqueous silver nitrate solution was added at an addition amount of silver nitrate of 4.74 g / min to make the silver potential +150 mV with respect to the saturated calomel electrode. After that, an aqueous solution of silver nitrate and an aqueous solution of halogen (containing 5.3% by weight of KI with respect to KBr) were added at an addition amount of silver nitrate of 4.74 g / min. At this time, the silver potential of the reaction solution was set to 0 mV with respect to the saturated calomel electrode. At this time, 152.3 g of silver nitrate was used. This emulsion was designated as Em-S.

An aqueous solution of silver nitrate and an aqueous solution of halogen (containing 5.3% by weight of KI relative to KBr) were added to Em-Q at an amount of silver nitrate of 4.74 g / min. At this time, the silver potential of the reaction solution was kept at 0 mV with respect to the saturated calomel electrode. At this time, 71.1 g of silver nitrate was used. 10 g of NaCl was added, and an aqueous solution of silver nitrate was added at an amount of 4.74 g / min to make the silver potential +150 mV with respect to the saturated calomel electrode. Then, an aqueous silver nitrate solution and an aqueous halogen solution (containing 5.3% by weight of KI relative to KBr) were added at a silver nitrate addition rate of 4.74 g / min. At this time, the silver potential of the reaction solution was set to 0 mV with respect to the saturated calomel electrode. At this time, add 8
Used 1.2 g. This emulsion was designated as Em-T.

Dye I-1 was added to Em-R, S and T for 1 mol of silver.
After adding 5 × 10 ⁻³ mol, the mixture was aged for 10 minutes. These emulsions were desalted, and gelatin and water were added to adjust the pH to 6.9 pAg 7.5 at 40 ° C. Compound II-1 at 64 ° C 1.4 × 10 to 1 mol of silver
^-3 mol was added, and optimum chemical sensitization was performed with sodium thiosulfate, potassium chloroaurate and sodium thiocyanate.

 The same coating as in Example-3 was performed.

These samples were left under conditions of 40 ° C. and 70% relative humidity for 14 hours, then exposed through a continuous wedge for 1/10 seconds, and subjected to the same color development process as in Example-3.

 The density of the treated sample was measured with a green filter.

The evaluation of the pressure characteristics was performed by the same method as in Example-1.

 The obtained results are shown in Table-7.

It can be seen from Table 7 that the pressure characteristics are remarkably improved by the present invention, but the position of the partially halogen-converted silver chloride layer inside the tabular grains has a great effect on the grain count.

Example-6 The effects on the pressure characteristics when the emulsion of the present invention is used in the blue-sensitive layer of a multilayer color photographic light-sensitive material will be described.

(Preparation of Samples 101 and 102) A multi-layer color photographic light-sensitive material comprising each layer having the composition shown below was prepared on an undercoated cellulose triacetate film support.

The amount coated amount <Composition of photosensitive layer> are expressed in units of g / m ² of silver for silver halide and colloidal silver, also couplers, the amount for the additives and gelatin, expressed in units of g / m ^2, The sensitizing dye is shown by the number of moles per mole of silver halide in the same layer.

1st layer: Antihalation layer Black colloidal silver 0.37 U-1 0.027 U-2 0.055 U-3 0.064 HBS-3 0.076 gelatin 2.81 2nd layer: Intermediate layer U-1 0.027 U-2 0.054 U-3 0.063 HBS- 3 0.076 Gelatin 1.52 Third layer: First red-sensitive emulsion layer Silver iodobromide emulsion Silver 0.43 (AgI 10 mol%, equivalent spherical diameter 0.9 μ, coefficient of variation 28.8%, diameter / thickness ratio 5.1) Silver iodobromide emulsion silver 0.11 (AgI 4 mol%, sphere equivalent diameter 0.6μ, coefficient of variation 36.6%, diameter / thickness ratio 3.4) Silver iodobromide emulsion silver 0.55 (AgI 2 mol%, sphere equivalent diameter 0.45μ, coefficient of variation 28%, diameter / thickness ratio 2.7 ) Sensitizing dye I 4.7 × 10 ^-3 C-1 0.14 C-2 0.15 C-3 0.08 C-5 0.08 HBS-1 0.06 HBS-2 0.13 C-10 0.14 Gelatin 1.66 Fourth layer: Second red-sensitive emulsion layer Silver iodobromide emulsion 0.73 (AgI 3.5 mol%, sphere equivalent diameter 0.35μ, coefficient of variation 10.6
%, Diameter / thickness ratio 1.0) Sensitizing dye I 4.0 × 10 ⁻³ C-1 0.27 C-2 0.28 C-3 0.07 C-4 0.11 HBS-1 0.12 HBS-2 0.24 C-10 0.007 Gelatin 2.34 Fifth layer : Intermediate layer Gelatin 0.92 Cpd-1 0.10 HBS-1 0.053 Dye I 0.075 U-4 0.023 U-5 0.036 HBS-4 7.7 × 10 ^-3 Sixth layer: First green emulsion layer Silver iodobromide emulsion Silver 0.48 ( AgI 3.5 mol%, sphere equivalent diameter 0.35μ, coefficient of variation 10.6
%, Diameter / thickness ratio 1.0) Sensitizing dye II 3.6 × 10 ^-3 Sensitizing dye III 1.7 × 10 ^-3 C-6 0.33 C-7 0.77 HBS-1 0.29 Gelatin 1.13 7th layer: 2nd green sensitive emulsion layer Silver iodobromide emulsion 0.21 (AgI 10 mol%, sphere equivalent diameter 0.9μ, coefficient of variation 28.8%, diameter / thickness ratio 5.1) Silver iodobromide emulsion silver 0.09 (AgI 4mol%, sphere equivalent diameter 0.6μ, coefficient of variation 36.6) %, Diameter / thickness ratio 3.4) Silver iodobromide emulsion 0.24 (AgI 2 mol%, equivalent spherical diameter 0.45μ, coefficient of variation 28%, diameter / thickness ratio 2.7) Sensitizing dye II 2.2 × 10 ^-3 Sensitizing dye III 1.0 × 10 ^-3 C-6 0.20 C-8 0.071 C-4 0.079 C-5 0.038 HBS-1 0.18 Gelatin 0.79 Eighth layer: Third green emulsion layer Silver iodobromide emulsion Silver 0.44 (AgI 10 mol%, Equivalent sphere diameter 1.2μ, coefficient of variation 29.4%,
Diameter / thickness ratio 6.3) Sensitizing dye II 5.6 × 10 ^-4 Sensitizing dye III 2.1 × 10 ^-4 Sensitizing dye IV 3.6 × 10 ^-5 C-6 0.036 C-5 0.020 HBS-1 0.032 Gelatin 0.34 9th layer : Yellow filter layer Yellow colloidal silver 0.11 Cpd-1 0.28 HBS-1 0.15 Gelatin 1.19 10th layer: 1st blue sensitive emulsion layer Silver iodobromide emulsion Silver 0.33 (AgI 1 mol%, equivalent spherical diameter 0.45μ, coefficient of variation 20.1 %, Diameter / thickness ratio 1.8) Sensitizing dye V 1.7 × 10 ⁻³ C-9 0.65 C-11 0.10 HBS-1 0.22 Gelatin 0.85 11th layer: 2nd blue-sensitive emulsion layer Silver iodobromide emulsion Silver 0.17 (enhanced (Sensing dye V is included in 3.0 × 10 ^-3 ) (AgI 4.1 mol%, sphere equivalent diameter 0.43μ, coefficient of variation 25%,
Diameter / thickness ratio 3.6) Silver iodochlorobromide emulsion Silver 0.21 (Em-A or Em-B) C-9 0.28 C-4 0.044 HBS-1 0.10 Gelatin 0.75 12th layer: 1st protective layer Gelatin 0.60 U-4 0.10 U-5 0.15 HBS-4 0.033 Dye II 0.15 13th layer: 2nd protective layer Polymethylmethacrylate particles Diameter about 1.5 μm 0.14 Gelatin 0.87 In addition to the above composition, each layer contains gelatin hardener H-1 and surfactant. Was added. The structural formulas of the compounds used are shown below.

Sensitizing dye HBS-1 tricresyl phosphate HBS-2 dioctyl phthalate HBS-3 dibutyl phthalate HBS-4 bis (2-ethylhexyl) phthalate Em-A or Em-B in Example-1 was used as the eleventh layer of the photosensitive layer. The used samples were samples 101 and 102, respectively.

These samples were left under conditions of 40 ° C. and 70% relative humidity for 14 hours, then exposed through a continuous wedge for 10 seconds and subjected to the development processing shown below to obtain characteristic curves of cyan, magenta and yellow color images. Regarding the characteristic curve of the yellow color image, the reciprocal of the exposure amount that gives an optical density higher than the fog density by 0.1 is shown by the relative sensitivity.

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

 Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Water washing 2 minutes 10 seconds Settling 4 minutes 20 seconds Water washing 3 minutes 15 seconds Stability 1 minute 05 seconds The composition of the treatment liquid used in each process is as follows. It was

Color developer Diethylenetriaminepentaacetic acid 1.0g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0g Sodium sulfite 4.0g Potassium carbonate 30.0g Potassium bromide 1.4g Potassium iodide 1.3mg Hydroxylamine sulfate 2.4g 4- (N- Ethyl-N-β-hydroxyethylamino) -2-methylaniline sulphate 4.5g Water added 1.0l pH 10.0 Bleaching solution Ethylenediaminetetraacetic acid ferric ammonium salt 100.0g Ethylenediaminetetraacetic acid disodium salt 10.0g Bromide Ammonium 150.0g Ammonium sulphate 10.0g Water added 1.0l pH6.0 Fixer Ethylenediaminetetraacetic acid disodium salt 1.0g Sodium sulfite 4.0g Ammonium thiosulfate aqueous solution (70%) 175.0ml Sodium bisulfite 4.6g Water added 1.0l pH6 .6 Stabilizer Formalin (40%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (plain Uniformity 10) 0.3g Water was added and 1.0l The pressure characteristics were evaluated as follows. 40% relative humidity
Fix the coated sample with the emulsion side facing up under the humidity control conditions of
The emulsion surface was scratched with metal needles having diameters of 1 mm, 0.1 mm and 0.01 mm. At this time, an appropriate load was applied on the metal needle. The scratching with the metal needle was performed before the development, and the change in the yellow density of the fogged portion in the scratched portion was measured with a microdensitometer.

 The obtained results are shown in Table-9.

It is apparent from Table 9 that the use of the emulsion according to the present invention makes it possible to obtain a light-sensitive material having high sensitivity and extremely excellent pressure resistance.

Example-7 The effects on the pressure characteristics when the emulsion of the present invention is used in the green-sensitive layer of a multilayer color photographic light-sensitive material will be described.

(Preparation of Samples 201 and 202) A multi-layer color photographic light-sensitive material comprising each layer having the composition shown below was prepared on an undercoated cellulose triacetate film support.

1st layer; antihalation layer Black colloidal silver 0.18 gelatin 0.40 2nd layer; intermediate layer 2,5-di-t-pentadecylhydroquinone 0.18 Ex-1 0.07 Ex-3 0.02 U-1 0.08 U-2 0.08 HBS- 1 0.10 HBS-2 0.02 Gelatin 1.04 Third layer (first red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 6 mol%, average grain size 0.8)
μ) Silver 0.55 Sensitizing dye I 6.9 × 10 ^-5 Sensitizing dye II 1.8 × 10 ^-5 Sensitizing dye III 3.1 × 10 ^-4 Sensitizing dye IV 4.0 × 10 ^-5 Ex-2 0.350 HBS-1 0.005 Ex- 11 0.008 Gelatin 1.20 4th layer (2nd red-sensitive emulsion layer) Silver iodobromide emulsion (8 mol% silver iodide, average grain size 0.85)
μ) Silver 1.20 Sensitizing dye I 5.1 × 10 ^-5 Sensitizing dye II 1.4 × 10 ^-5 Sensitizing dye III 2.3 × 10 ^-4 Sensitizing dye IV 3.0 × 10 ^-5 Ex-2 0.300 Ex-3 0.050 Ex- 10 0.004 HBS-2 0.050 Gelatin 1.30 Fifth layer (third red-sensitive emulsion layer) Silver iodobromide emulsion (14 mol% silver iodide, average grain size 1.5)
μ) Silver 1.60 Sensitizing dye IX 5.4 × 10 ^-5 Sensitizing dye II 1.4 × 10 ^-5 Sensitizing dye III 2.4 × 10 ^-4 Sensitizing dye IV 3.1 × 10 ^-5 Ex-5 0.150 Ex-3 0.055 Ex- 4 0.060 Ex-11 0.005 HBS-1 0.32 Gelatin 1.63 6th layer (intermediate layer) Gelatin 1.06 7th layer (1st green emulsion layer) Em-J or Em-K silver 0.40 Ex-6 0.260 Ex-1 0.021 Ex -7 0.030 Ex-8 0.025 HBS-1 0.100 Gelatin 0.75 Eighth layer (second green emulsion layer) Silver iodobromide emulsion (9 mol% silver iodide, average grain size 0.85)
μ) Silver 0.80 Sensitizing dye V 2.1 × 10 ^-5 Sensitizing dye VI 7.0 × 10 ^-5 Sensitizing dye VII 2.6 × 10 ^-4 Ex-6 0.150 Ex-8 0.010 Ex-1 0.008 Ex-7 0.012 HBS-1 0.60 Gelatin 1.10 9th layer (3rd green emulsion layer) Silver iodobromide emulsion (12 mol% silver iodide, average grain size 1.3)
μ) Silver 1.2 Sensitizing dye V 3.5 × 10 ^-5 Sensitizing dye VI 8.0 × 10 ^-5 Sensitizing dye VII 3.0 × 10 ^-4 Ex-6 0.065 Ex-1 0.025 HBS-2 0.55 Gelatin 1.74 10th layer (yellow) Filter layer) Yellow colloidal silver 0.052,5-di-t-pentadecylhydroquinone 0.03 Gelatin 0.95 11th layer (first blue sensitive emulsion layer) Silver iodobromide emulsion (8 mol% silver iodide, average grain size 0.8)
μ) Silver 0.24 Sensitizing dye VIII 0.5 × 10 ⁻⁴ Ex-9 0.85 Ex-8 0.12 HBS-2 0.28 Gelatin 1.28 12th layer (2nd blue-sensitive emulsion layer) Silver iodobromide emulsion (Silver iodide 10 mol% , Average particle size 1.0
μ) Silver 0.45 Sensitizing dye VIII 2.1 × 10 ⁻⁴ Ex-9 0.20 HBS-2 0.03 Gelatin 0.46 13th layer (3rd blue emulsion layer) Silver iodobromide emulsion (10 mol% silver iodide, average grain size) 1.8
μ) Silver 0.77 Sensitizing dye VIII 2.2 × 10 ⁻⁴ Ex-9 0.20 HBS-2 0.07 Gelatin 0.69 14th layer (first protective layer) Silver iodobromide emulsion (1 mol% silver iodide, average particle size 0.07)
μ) Silver 0.5 U-1 0.11 U-2 0.17 HBS-1 0.90 Gelatin 1.00 Fifteenth layer (second protective layer) Polymethyl acrylate particles (diameter about 1.5 μm) 0.54 S-1 0.05 S-2 0.20 Gelatin 0.72 Each layer In addition to the above components, gelatin hardener H-1 and a surfactant were added.

The chemical structural formula or chemical name of the compound used in the present invention is
I will show you later.

HBS-1 tricresyl phosphate HBS-2 dibutyl phthalate Sensitizing dye Samples 201 and 202 were prepared by using Em-J or Em-K in Example-4 as the seventh layer of the photosensitive layer.

After leaving these samples under the conditions of 40 ° C and 70% relative humidity for 14 hours, fix one end with the emulsion surface inside and set the diameter to 10
It was bent by rotating 180 mm along a stainless steel pipe of mm. Then, the same developing treatment as in Example-7 was performed to measure the change in fog density at the bent portion of the magenta color image.

The obtained results are shown in Table-10. The emulsion of the present invention reduced the increase in pressure fog.

The characteristic curve of a magenta color image obtained by performing the same development process after exposing it for 1/100 second through a continuous wedge is the sample.
As compared with 201, the sample 202 showed good gradation on the high density side.

Example-9 The effect on the sensitivity and pressure characteristics when the emulsion of the present invention is used in the red-sensitive layer of a multilayer color photographic light-sensitive material will be described.

(Preparation of Samples 301, 302, 303 and 304) On the undercoated cellulose triacetate film support, a multi-layer color photographic light-sensitive material comprising each layer having the composition shown below was prepared.

First layer (antihalation layer) Black colloidal silver 0.2 Gelatin 1.3 ExM-9 0.06 UV-1 0.03 UV-2 0.06 UV-3 0.06 Solv-1 0.15 Solv-2 0.15 Solv-3 0.05 Second layer (intermediate layer) Solv -1 0.1 Solv-2 0.1 Gelatin 1.0 UV-1 0.03 ExC-4 0.02 Third layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, uniform AgI type, equivalent spherical diameter 0.5)
μ, coefficient of variation of equivalent sphere diameter 20%, plate-like particles, diameter / thickness ratio
3.0) Coating silver amount 1.2 Silver iodobromide emulsion (AgI 3 mol%, uniform AgI type, spherical equivalent diameter 0.3
μ, coefficient of variation of equivalent spherical diameter 15%, spherical particles, diameter / thickness ratio
1.0) Silver coating amount 0.6 Gelatin 1.0 ExS-1 4 × 10 ^-4 ExS-2 5 × 10 ^-5 ExC-1 0.05 ExC-2 0.50 ExC-3 0.03 ExC-4 0.12 ExC-5 0.01 4th layer (high sensitivity) Red-sensitive emulsion layer) Em-C, D, E or F coating silver amount 0.7 Gelatin 1.0 ExS-1 3 × 10 ^-4 ExS-2 2.3 × 10 ^-5 ExC-6 0.11 ExC-7 0.05 ExC-4 0.05 Solv- 1 0.05 Solv-3 0.05 5th layer (intermediate layer) Gelatin 0.5 Cpd-1 0.1 Solv-1 0.05 6th layer (low sensitivity green emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, surface high AgI type, sphere) Equivalent diameter
0.5μ, variation coefficient of equivalent sphere diameter 15%, plate-like grain, diameter / thickness ratio 4.0) Coating silver amount 0.35 Silver iodobromide emulsion (AgI 3 mol%, uniform AgI type, equivalent sphere diameter 0.3)
μ, coefficient of variation of equivalent sphere diameter 25%, spherical particles, diameter / thickness ratio
1.0) Silver coating amount 0.20 Gelatin 1.0 ExS-3 5 × 10 ^-4 ExS-4 3 × 10 ^-4 ExS-5 1 × 10 ^-4 ExM-8 0.4 ExM-9 0.07 ExM-10 0.03 ExY-11 0.03 Solv- 1 0.3 Solv-4 0.05 7th layer (high sensitivity green emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, internal high AgI type, equivalent spherical diameter)
0.7μ, coefficient of variation of equivalent sphere diameter 20%, plate-shaped particles, diameter / thickness ratio 5.0) Coating silver amount 0.8 ExS-3 5 × 10 ^-4 ExS-4 3 × 10 ^-4 ExS-5 1 × 10 ^-4 ExM-8 0.1 ExM-9 0.02 ExY-11 0.03 ExC-2 0.03 ExM-14 0.01 Solv-1 0.2 Solv-4 0.01 8th layer (intermediate layer) Gelatin 0.5 Cpd-1 0.05 Solv-1 0.02 9th layer (multilayer) Donor layer of effect) Silver iodobromide emulsion (AgI 2 mol%, internal high AgI type, equivalent spherical diameter)
1.0μ, coefficient of variation of equivalent sphere diameter 15%, tabular grains, diameter / thickness ratio 6.0) Silver coating amount 0.35 Silver iodobromide emulsion (AgI 2 mol%, internal high AgI type, equivalent sphere diameter)
0.4μ, coefficient of variation of equivalent sphere diameter 20%, plate-shaped particles, diameter / thickness ratio 6.0) Coating silver amount 0.20 Gelatin 0.5 ExS-3 8 × 10 ^-4 ExY-13 0.11 ExM-12 0.03 ExM-14 0.10 Solv- 1 0.20 10th layer (yellow filter layer) Yellow colloidal silver 0.05 Gelatin 0.5 Cpd-2 0.13 Cpd-1 0.10 11th layer (low sensitivity blue emulsion layer) Silver iodobromide emulsion (AgI 4.5 mol%, uniform AgI type) , Sphere equivalent diameter
0.7μ, variation coefficient of equivalent sphere diameter 15%, plate-like grain, diameter / thickness ratio 7.0) Coating silver amount 0.3 Silver iodobromide emulsion (AgI 3 mol%, uniform AgI type, equivalent sphere diameter 0.3)
μ, coefficient of variation of sphere equivalent diameter 25%, plate-like particles, diameter / thickness ratio
7.0) Coating silver amount 0.15 Gelatin 1.6 ExS-6 2 × 10 ^-4 ExC-16 0.05 ExC-2 0.10 ExC-3 0.02 ExY-13 0.07 ExY-15 0.5 ExY-17 1.0 Solv-1 0.20 12th layer (high sensitivity) Blue-sensitive emulsion layer) Silver iodobromide emulsion (AgI 10% mol, internal high AgI type, equivalent spherical diameter)
1.0μ, coefficient of variation of equivalent spherical diameter 25%, irregular particles, diameter /
Thickness ratio 2.0) Coating amount 0.5 Gelatin 0.5 ExS-6 1 × 10 ^-4 ExY-15 0.20 ExY-13 0.01 Solv-1 0.10 13th layer (1st protective layer) Gelatin 0.8 UV-4 0.1 UV-5 0.15 Solv -1 0.01 Solv-2 0.01 14th layer (2nd protective layer) Fine grain silver bromide emulsion (12 mol, 0.07μ) 0.5 Gelatin 0.45 Polymethylmethacrylate grain diameter 1.5μ 0.2 H-1 0.4 Cpd-3 0.5 Cpd-4 0.5 In addition to the above components, an emulsion stabilizer Cpd-3 surfactant Cpd-4 was added to each layer as a coating aid.

 In addition, the following compounds Cpd-5 to Cpd-6 were added.

Solv-1 Tricresyl Phosphate Solv-2 Dibutyl Phthalate Em-C or Em-D or Em-E in Example-2 or
Each of Em-F used as the first fourth layer of the above-mentioned photosensitive layer,
Samples 301, 302, 303 and 304 were used.

After leaving these samples under conditions of 40 ° C and 70% relative humidity for 14 hours, they were exposed through a continuous wedge for 1/100 seconds,
The same developing process as in Example-7 was performed to obtain characteristic curves of cyan, magenta and yellow color images. The reciprocal of the exposure amount that gives an optical density higher than the fog density by 0.1 is shown as relative sensitivity in the characteristic curve of the cyan image. The pressure characteristics were evaluated in the same manner as in Example-8.

 The results are shown in Table-11.

Table 11 clearly shows that the emulsion of the present invention can provide a sensitive material having high sensitivity and excellent pressure characteristics.

(Effect of the Invention) According to the present invention, it is possible to obtain an emulsion composed of silver halide grains having high sensitivity and good granularity with improved pressure characteristics.

A silver halide having improved sensitivity including improvement of color sensitization efficiency by a sensitizing dye, improved sensitivity / granularity relationship, improved sharpness, improved covering power and improved pressure characteristics according to the present invention. An emulsion can be obtained.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a 50,000-fold low-temperature transmission electron micrograph showing the crystal structure of Em-A silver halide grains prepared in Example 1. FIG. 2 is a 50,000-fold low-temperature transmission electron micrograph showing the crystal structure of the silver halide grains of Em-B prepared in Example 1.

Front page continued (72) Inventor Hiroshi Ayado 210 Nakanuma, Minamiashigara City, Kanagawa Fuji Photo Film Co., Ltd. Examiner Kayoko Yasuda (56) References JP 62-18538 (JP, A) JP 62-89953 (JP, A) JP-A-1-102548 (JP, A) JP-A-61-2148 (JP, A) JP-A-62-108240 (JP, A) JP-A-59-24841 (JP, A) Kai 60-136735 (JP, A) JP 61-122641 (JP, A) JP 62-24243 (JP, A)

Claims (1)

[Claims] 1. A photographic emulsion containing silver bromide-based grains, wherein the grains have a silver bromide-based layer inside the grains.
It has a silver chloride or silver citrate containing layer on it, and the silver chloride or silver citrate containing layer is a part of which is converted to halogen after forming the layer, and further a silver bromide-based layer is further formed thereon. A silver halide photographic emulsion having a layer consisting of