JPH0611789A - Silver halide photographic emulsion and its manufacture - Google Patents

Abstract

PURPOSE:To obtain the silver halide emulsion high in sensitivity and small in fog and its manufacturing method and the silver halide photographic sensitive material improved in sensitivity and fog. CONSTITUTION:The photographic sensitive material is formed by adjusting a silver halide emulsion to a temperature of 70 deg.C, adding a chemical sensitizer, such as N,N-dimethylselenourea in an amount of 1.3X10<-6>mol/mol of silver halide in a constant flow rate in 60min, after that, adding a mixture of aqueous solutions of chloroauric acid and ammonium thiocyanate, further ripening it for 60min to form the silver halide emulsion of aggregations of >=2 compound molecules for composing chemically sensitizing nuclei, and spectrally sensitizing them, adding various kinds of photographic additives, and coating a support.

Description

Detailed Description of the Invention

[0001]

The present invention relates to silver halide (hereinafter AgX
Specifically, regarding the photographic emulsion, the chemical sensitized nuclei formed on the AgX grains have improved sensitivity because the constituent compound molecules have aggregates of two or more molecules.
It concerns photographic emulsions.

[0002]

It is well known to chemically sensitize an AgX photographic emulsion with a sulfur sensitizer, and the observation of the silver sulfide formed at this time by an electron microscope is, for example, G.C.Fernel, P.B. Flint, D.C. Birch (Journal of Photographic Science
25, p. 203 (1977)).

Their observations indicate the presence of numerous silver sulfide nuclei on AgX grains.

In the case of sulfur sensitization, the photographic sensitivity is basically determined by the silver sulfide formation site, number and density, size and composition, and it is necessary to control these to the state where latent image formation efficiency is highest. These control factors are the same for sulfur sensitization, gold sulfur sensitization, and noble metal sensitization, and it is known that there are optimum conditions in combination with AgX grains.

However, in the conventionally known chemical sensitization method, the technical means for controlling the formation site, number and density, size, composition, etc. of the chemical sensitization nuclei are incomplete, and further all parameters are controlled. It was very difficult. Among these, the parameter that particularly controls the sensitivity is the size of the chemical sensitization nucleus, and the compound molecule that constitutes the chemical sensitization nucleus formed on the AgX particles is
A technique relating to size regulation such as that of the present invention that has an aggregate in which two or more molecules are aggregated has not yet been disclosed.

For example, Japanese Patent Application Laid-Open No. 61-93447 describes that silver sulfide, gold sulfide, or a mixture thereof is selectively grown. This is a rule concerning the site for forming chemical sensitized nuclei. Yes, it is not a dominant parameter for improving sensitivity and is completely separate from the present invention.

Further, JP-A-63-305343 and 64-26838.
No. 64-77047, there is a content about the site regulation of the development starting point, but the development starting point is more strongly influenced by the developability than the chemical sensitized nuclei, and what kind of grain shape and what kind of chemistry It is common knowledge in the art that most of the particles are developed from the apex of the grains even if the sensitization method is applied, and it has nothing to do with the novel chemical sensitization method regarding the size of the chemical sensitization nucleus of the present invention. .

Regarding the site for forming the chemically sensitized nuclei, JP-A-64-40938, JP-A-64-62631, JP-A-64-62632,
No. 64-74540, JP-A No. 1-158425, No. 2-34, No. 2-2989
Although there are many descriptions such as No. 35, these specify only the formation site of the chemical sensitized nuclei, and there is no description about the size of the chemically sensitized nuclei that is most important for improving the sensitivity. This is completely different from the new chemical sensitization method regarding the size of the chemically sensitized nucleus. The present invention intends to solve a large improvement in sensitivity, which cannot be solved by the development starting point and the site for forming chemically sensitized nuclei as described above, by defining the size of the chemically sensitized nuclei. .

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide an AgX photographic emulsion having high sensitivity and a method for producing the same by controlling the size of chemically sensitized nuclei, and secondly, the sensitivity. To provide a high-quality AgX photographic light-sensitive material.

[0010]

As a result of intensive studies, the present inventors have found that the object of the present invention can be achieved by the following.

(1) A compound molecule in which the chemically sensitized nucleus formed on the photosensitive silver halide grain contains at least one atom selected from sulfur, selenium, tellurium, and noble metal VIII of the periodic table. It consists of an assembly of two or more molecules,
And the amount of the compound molecule is 1 × per mol of silver halide.
A silver halide photographic emulsion characterized by being 10 ^-4 mol or less.

(2) As the chemical sensitizer, at least one selected from thiourea compounds, selenourea compounds, and dithiacarbamic acid compounds is used, and the silver halide described in (1) is used. Photographic emulsion.

(3) The chemical sensitizer is added in a plurality of divided portions or is added continuously (1)
A method for producing the described silver halide photographic emulsion.

(4) In the silver halide photographic emulsion according to (1), a chemical sensitizer is added under a temperature condition of 50 ° C. or higher, and a high temperature of 70 ° C. or higher is passed during ripening. Production method.

(5) The method for producing a silver halide photographic emulsion as described in (1), which comprises chemically ripening in the presence of at least one selected from thiocyanate compounds, thioethers and telluroethers.

(6) The method for producing a silver halide photographic emulsion according to (1), wherein the chemical ripening is performed in the presence of an azaindene or a heterocyclic compound having a mercapto group.

(7) The grains are composed of (111) faces and (100) faces, and the ratio of one face to the whole face is 40% or less. The method for producing a silver halide photographic emulsion according to (1) above, wherein

(8) Lattice defects or at least one of silver sulfide nuclei, gold nuclei, gold sulfide silver nuclei and silver nuclei are formed in advance in the vicinity of the ridges or vertices of silver halide grains, and then a chemical sensitizer is added. (1) The method for producing a silver halide photographic emulsion as described in (1) above.

(9) The method for producing a silver halide photographic emulsion according to (1), wherein chemically sensitized nuclei are formed in advance and then the chemically sensitized nuclei are added to the emulsion.

In the present invention, the term "comprising two or more compound molecules constituting the chemically sensitized nucleus" means that, for example, in the case of silver sulfide, two molecules of silver sulfide (Ag ₂ S) are present on the surface of AgX grains. It may be an aggregate, or an aggregate of three or more molecules, which may be epitaxially grown as a silver sulfide crystal, and includes cases where chemical sensitized nuclei are close to each other and potential energy overlaps.

The size of two molecules of silver sulfide is about 6Å in the longitudinal direction.
And, having a size of two or more molecules of silver sulfide means that the diameter of the projected area converted to a circle is 6 Å or more.

Further, when two or more molecules are defined, it means a case in which two or more compound molecules on AgX particles, which can be chemically sensitized nuclei even in a single molecule, are aggregated. In addition, it does not matter if the chemically sensitized nuclei of two or more molecules overlap in the vertical direction of the base of the AgX particles.

In the case of silver selenide, silver telluride and silver gold sulfide nucleus, the definition of two or more molecules is the same.

The composition of the chemically sensitized nuclei formed by the chemical sensitization method and the number of molecules of the compounds constituting the chemically sensitized nuclei may have a distribution, but the composition, number of molecules and size are all It may be considered by the average composition, average number of constituent molecules, and average size of the chemically sensitized nucleus.

The preferred assembly of the chemically sensitized nuclei of the present invention is 2
The number of molecules is not less than 3 but more preferably not less than 3 and more preferably not less than 4.

However, since the size becomes large and fog occurs, it is preferable to make the size as large as possible in a region where the increase in fog is small.

Further, these individual chemical sensitizing nuclei are preferably monodisperse in their composition, size and distribution.

Further, the number of chemically sensitized nuclei of the present invention is preferably 20% or more, more preferably 50% or more, and further preferably 70% or more in the whole.

Although it is not clearly understood why a large improvement in sensitivity is achieved when the compound molecules constituting the chemical constituent nucleus have an aggregate of two or more molecules, the size of the chemical sensitization nucleus is not clear. It is considered that this is because the electron capture cross-sectional area increases as well as the value increases, and efficient latent image formation is performed.

It is surprising that the phenomenon that the sensitivity of the silver halide emulsion is significantly improved is not seen in the selective growth of chemically sensitized nuclei as disclosed in JP-A-61-93447. It should be a discovery.

It can be observed by the following method that the chemical sensitizing nuclei have an aggregate in which two or more molecules of the constituent compounds are aggregated. There are roughly two types of observations, one is electron microscope observation and the other is spectroscopic observation. Both are useful, but visual observation with an electron microscope is more effective.

It is possible to use the transmission electron microscope observation method by the gelatin foreskin method performed by Farnell or the like, or the carbon replica method. The size of the chemically sensitized nuclei was examined by these methods, and the average size of the chemically sensitized nuclei on the negative and the print was processed by an image processor, and two or more molecules of the compounds constituting the chemically sensitized nuclei were aggregated. It can be easily determined whether it is an aggregate.

For example, Hitachi H-600 type, JD manufactured by JEOL Ltd.
The EH-2000FX can be used with the acceleration voltage that allows the clearest observation.

Below, the AgX formed on the AgX particles of the present invention
From a compound molecule containing at least one atom selected from the group consisting of sulfur, selenium, tellurium, gold, the periodic table, and Group VIII noble metals (hereinafter referred to as Group VIII noble metals) in an amount of 1 × 10 ⁻⁴ mol or less per mol. The chemical sensitization nuclei described below describe in detail the eight conditions for the molecule of the compound to have an aggregate of two or more molecules.

Structure of Sensitizer As the sensitizer, any compound containing a sulfur atom, a selenium atom, and a tellurium atom can be selected. For example, hypo, inorganic sulfur compounds, thioureas compounds, rhodanin compounds, oxazolidine compounds, polysulfide compounds. , Selenoureas, dithiacarbamic acids and the like. Among them, thioureas, selenoureas, and dithiacarbamic acids are preferable in order to easily form an aggregate in which two or more molecules are aggregated, and compounds having a cyclic structure are more preferable. Examples of the compound containing a Group VIII noble metal atom include ruthenium chloride, rhodium chloride, potassium tetrathiopalladium (II) and potassium hexachloroplatinate (IV) -acid.

Method of adding chemical sensitizer The above chemical sensitizer reacts with AgX to form silver sulfide, silver selenide, silver telluride, silver silver sulfide, gold silver selenide, gold silver telluride. In order to grow the chemically sensitized nuclei, it is necessary to make the system a feed rate-controlled system and to perform the formation reaction of these sulfides extremely slowly. For this reason, the preferred method is to add the sensitizer in a plurality of divided portions, and the most preferred method is to add it continuously.

When dividedly or continuously added in a plurality of times, the respective addition amounts may be the same or different, and more preferably the latter addition amount is the same as or larger than the first addition amount. The growth of the chemical sensitizing nuclei by this division and continuous addition of the sensitizer varies depending on the type of the sulfur sensitizer or the emulsion used, but it is preferable to add slowly for 10 minutes or more, preferably for 1 hour or more.

In the chemical sensitization, the amount of sulfur sensitizer used (hereinafter, selenium compound and tellurium compound are also included as sulfur sensitizer) is in the range of 10 ^-8 to 10 ^-4 mol per mol of silver halide. You can Further more preferably 10 ^-7
It is from 10 to ⁴ mol. A precursor type compound may be used in order to make the reaction rate-controlled, or may be added as a mixture with a compound that forms an inclusion complex such as cyclodextrin. Also, the gold sensitizer used or VIII
Group noble metal compounds are also used in an amount of 10 per mol of silver halide.
^-8 mol to 10 ^-4 mol range is preferred, more preferably
It is from 10 ^-7 mol to 10 ^-4 mol.

These sulfur, selenium, tellurium, gold and VIII
There is no particular limitation on the order of addition of the compound of the group noble metal, and any compound may be added first, but if possible, it is preferable to add the compound of sulfur, selenium, and tellurium first.

Environment for chemical ripening The environment for adding and aging the sensitizer cannot be uniquely determined due to the adsorption condition of the sensitizing dye, but the temperature is preferably 50 ° C. or higher. It is preferable that the chemical sensitization nucleus is aged at a high temperature so that the compound molecules constituting the chemical sensitization nucleus have an aggregate of two or more molecules. This is the chemical sensitization at a low temperature described in JP-A-61-93447. This is the reason why the present invention is completely different from the selective growth of nuclei. Furthermore, 65 ° C or higher is preferable and 75 ° C
The above is the most preferable.

The temperature described here may be passed through this state even once, and preferably at least this state is passed.
It is important to continue the treatment for 10 minutes or more, and it is preferable that the temperature in the initial stage of ripening is lower than that in the latter stage in view of the uniformity of the formation of the chemically sensitized nuclei between grains. Further, when the sensitizers are continuously added, it is preferable that the initial temperature of the addition is lower than or the same as that in the middle and late stages, since the aging is performed simultaneously during the addition. Further, the electric potential of the reaction tank is preferably 7 to 11 in pAg, more preferably 8 to 10, and further preferably 8 to 9.5. The pH is preferably 5.0 to 8.0. In particular, a combination of pAg of 8.5 or more and pH of 5.5 or less is preferable in order to make an aggregate of two or more compound molecules constituting the chemical sensitization nucleus.

Dissolution of silver halide grains or chemically sensitized nuclei It is preferable to use a solvent in order to increase the size of the chemically sensitized nuclei. Examples of this solvent include thiocyanates, thioethers, telluroethers, and the like.
Specifically, KSCN, NH ₄ SCN and the like are preferable. These may be effective before or after the addition of the sensitizer, and are effective at the same time or after, but more preferably before the addition of the sulfur sensitizer. The growth mechanism of the chemical sensitized nuclei by this solvent is not clear, but the surface of the silver halide grain is roughened to form the growth starting point of the chemical sensitized nuclei, or the single molecule of the chemical sensitized nuclei is dissolved. It is considered to be a thing.

Coating of Surface with Adsorbate It is possible to coat the surface of the silver halide grain with an adsorbate, reduce the area where the chemically sensitized nuclei are formed, and grow the chemically sensitized nuclei. For this purpose, use of a sensitizing dye is preferable, but adsorbates such as azaindenes and mercapto group-containing heterocyclic compounds are also effective.

Specifically, tetraazaindene and phenylmercaptotetrazole are preferable.

The coating of the grain surface with the adsorbate causes the growth of the chemical sensitizing nucleus most when it is carried out before the addition of the sulfur sensitizer, but after the addition of the chemical sensitizer or after the chemical sensitizer is added. Is effective even during continuous addition of
By controlling the timing of addition, chemically sensitized nuclei of any size can be formed. Further, in the case of a (100) face-selective sulfur sensitizer that forms silver sulfide on the (100) face, the adsorbate is preferably a (111) face adsorbate such as tetraazaindene.

Similarly, in the case of the sulfur sensitizer of the (111) plane selective type, the adsorbate is preferably the (100) plane adsorption type.

Chemically Sensitized Nucleation Site The chemically sensitized nuclei can be grown depending on the shape, crystal habit and halide composition of silver halide grains. For example, using silver halide grains consisting of (100) and (111) faces,
By combining the total area and the surface-selective sensitizer, it is possible to form an aggregate in which two or more molecules of the chemical sensitizing nucleus are assembled.

In the case of sodium thiosulfate, it is a (111) selective type, and since silver sulfide formation occurs on the (111) plane,
Use a cubic emulsion composed of (0) faces, or (1
It is preferable to use a tetradecahedral emulsion having both 11) and (100) faces.

In the case of an octahedral emulsion having a (111) plane, the grain surface is coated with a sensitizing dye as described in
It is preferable to form silver sulfide only in the vicinity of the ridgeline from the viewpoint of growth of chemically sensitized nuclei.

In the case of a (100) selective sulfur sensitizer such as triethylthiourea, an octahedral emulsion, a tetradecahedral emulsion or a tabular emulsion having a low ratio of the (100) plane to the total surface area is preferable.

This ratio is preferably 50% or less, more preferably 20% or less.

Formation of Growth Starting Point A small number of silver sulfides, gold sulfides, gold silver sulfides and metals are previously prepared.
Defects such as silver nuclei and lattice mismatches, kinks, etc. can be formed on the surface of silver halide grains, and then a chemical sensitizer can be added to cause the growth of chemically sensitized nuclei. In particular, silver sulfide, gold sulfide, silver gold sulfide, silver nuclei and the like are preferable, but defects formed in advance on the surface of silver halide may be used, and if the metal is Fe, Ir,
Pd, Cd, Re, Os and the like are preferable.

The formation site of this growth starting point is particularly preferably near the ridges and vertices of the silver halide grains.

Particularly in the case of silver nuclei, the reduction sensitization method well known to those skilled in the art can be easily used.

Method of Growing Chemically Sensitized Nuclei A method of previously preparing chemically sensitized nuclei and then adding the product to a silver halide emulsion can also be used.

As a method for growing chemically sensitized nuclei, a method in which fine grain silver halide sensitized with sulfur or gold and sulfur and gold are mixed and dissolved with photosensitive silver halide and kept at high temperature for a long time Can be used.

It is also possible to mix an aqueous solution of silver sulfate with an aqueous solution of sulfur sensitizer and an aqueous solution of sulfur and gold sensitizer to prepare silver sulfide and gold silver sulfide gold sol and add them.

The ultrafine silver sulfide and gold sulfide silver sol are particularly preferable because they can control any particle size and particle size distribution.

The compounds containing sulfur, selenium, tellurium and the like according to the present invention include, for example, Chem. Rev., 55,181 (1955) and Chem.Be.
r., 63,208 (1930), J.Org.Chem., 36,3895 (1971), J.Che
It can be easily synthesized using the method described in m.Soc., 1957, 2999, etc.

The gold-containing compound according to the present invention is Bull.C.
hem.Soc.Japan., 48 (3), 1024-9 (1975), J.Inorg, Nucl.C
hem., 38 (1), 7-11 (1976), Transition Met. Chem., 2 (6),
224 to 227 (1977) and the method described in JP-A 1-147537.

A compound containing a Group VIII noble metal is Aldrich Ch
They are sold at emical Company, Johonson Mathey Company, etc. and can be easily purchased.

Sulfur, selenium, tellurium and VI according to the invention
The compound containing a Group II noble metal is preferably added to the silver halide grain emulsion after being dissolved in water or a water-miscible solvent such as methanol, ethanol or fluoroalcohol alone or in a mixed solvent. When the compound is poorly soluble in a suitable solvent, it is preferable to add it in the form of a dispersion.

The core of the silver halide grains contained in the emulsion of the present invention consists essentially of silver iodobromide, which consists essentially of silver iodobromide containing 5 mol% or more of silver iodide. It is preferably a core. The silver halide grains are composed of a core and a shell which covers the core and is composed essentially of silver iodobromide or silver bromide having a silver iodide content lower than the silver iodide content of the core. . The silver iodide content of the core is more preferably 10 mol% or more, and most preferably 20 mol% or more and 44 mol% or less. The silver iodide content of the shell is preferably 5 mol% or less.

The core may contain silver iodide uniformly, or may have a multiple structure composed of phases having different silver iodide contents. In the latter case, the silver iodide content of the phase having the highest silver iodide content is 5 mol% or more, more preferably 10 mol% or more, and the silver iodide content of the shell is the core. Of the highest silver iodide content phase.

In the present invention, "consisting essentially of silver iodobromide" mainly comprises silver iodobromide, but other components may be contained, for example, up to about 1 mol%. Means

A more preferred embodiment of the silver halide grains used in the photographic emulsion layer of the silver halide photographic light-sensitive material of the present invention is a halogenation using Cu Kβ rays in the diffraction angle (2θ) range of 38 to 42 °. When the curve of the diffraction intensity vs. the diffraction angle of the silver (220) plane was obtained, two diffraction maxima, a diffraction peak corresponding to the core part and a peak corresponding to the shell part, and one minimum appeared between them. And the diffraction intensity corresponding to the core is
That is, the particles have a structure that is 1/10 to 3/1 of that of the shell part. Particularly preferably, the diffraction intensity ratio is 1 /
5 to 3/1, and more preferably 1/3 to 3/1.

By having such a double structure and an aggregate in which two or more compound molecules constituting the chemical sensitizing nuclei are aggregated as in the present invention, it is possible to improve the iodide without delaying the developing rate. It becomes possible to use a silver iodobromide emulsion having a silver content, and a light-sensitive material having excellent graininess can be achieved even with a small coating amount of silver.

Another preferred embodiment of the silver halide grain contained in the emulsion of the present invention has a silver iodobromide phase having a silver iodide content of 10 to 40 mol% which forms a core inside the grain. ,
This is the case where the silver iodobromide phase is covered with a silver halide phase containing a lower silver iodide which forms the shell portion, and the surface of the grain further contains 5 mol% or more of silver iodide. The silver iodide composition contained in the shell part may be uniform or non-uniform.
The surface containing 5 mol% or more of silver iodide means that the average content of silver iodide on the grain surface measured by the XPS method is 5 mol% or more. Preferably, the average content of silver iodide on the surface is 7 mol% or more and 15 mol% or less. The silver halide grains are described in detail in JP-A-63-106745. Silver halide grains having a silver iodide content of the outermost surface layer higher than that of the intermediate layer are also included in the core / shell grains of the present invention, but the silver halide having the chemically sensitized nuclei having the features of the present invention is formed. For the first time by using particles,
Higher sensitivity could be achieved. The silver halide grains are preferable because they have good graininess.

Another preferred embodiment of the silver halide grains contained in the emulsion of the present invention is substantially silver iodobromide and / or
Alternatively, an inner core made of silver iodide forms a core, and a plurality of outer shells provided outside the inner core and substantially made of silver bromide and / or silver iodobromide (the outer shell forms a shell) A silver halide grain having a silver iodide content of 10 mol% or less in the outermost shell and a silver iodide content of 6 mol% or more higher than that of the outermost shell. A containing shell is provided inside the outermost shell, and an intermediate shell having a silver iodide content intermediate between these outer shells is provided between the outermost shell and the high silver iodide containing shell. And the silver iodide content of the middle shell is 3 mol% or more higher than that of the outermost shell, and the silver iodide content of the high silver iodide shell is 3 mol% or more higher than that of the middle shell. is there. The silver halide grains are described in JP-A-61-24515.
It is described in detail in No. 1.

In the emulsion of the present invention, it is particularly preferable that the silver iodide content of individual silver halide grains is uniform from the viewpoint of uniformity of chemical sensitization and spectral sensitization.

The emulsion having a good uniformity of the silver iodide content as described above can be constituted by various means for improving the uniformity and can be achieved, for example, by devising the production conditions of the silver halide emulsion. For example, as shown in Japanese Patent Application No. 63-224002, a method for producing an emulsion in which iodide ions are supplied by silver iodide fine particles, or silver iodobromide fine particles as disclosed in JP-A 1-183417 are seeded by Ostwald ripening. A method of growing the particles is useful.

The silver halide composition preferable as the silver halide constituting the emulsion of the present invention is silver iodobromide containing 30 mol% or less of silver iodide. Particularly preferred is silver iodobromide containing 2 to 20 mol% of silver iodide.

In order to achieve both high sensitivity and high image quality, the average silver iodide content of silver halide in all emulsion layers should be 8 mol as described in JP-A-60-128443. % Or more is preferable. It is known that the graininess is remarkably improved by increasing the average silver iodide content of silver halide. However, when the silver iodide content exceeds a certain level, the development speed is delayed, the desilvering and the fixing speed are increased. Defects such as delays will appear. In this respect, as described above, the emulsion of the present invention overcomes this problem, can increase the average silver iodide content, and has solved such a problem.

To form the light-sensitive material of the present invention, emulsions other than the emulsion of the present invention can be used in combination, if necessary. In this case, the silver halide composition of the emulsion used in combination is arbitrary, and for example, silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, silver chloride, or the like, or a mixture thereof is used. Good.

As the emulsion of the present invention or an emulsion other than the present invention which is used in combination as necessary (hereinafter, collectively referred to as "emulsion used in the present invention"), the coefficient of variation of the average grain size (JP-A-
A monodisperse emulsion having a ratio of 16% or less according to the formula described in 59-152438) is preferred.

The shape of the silver halide grains in the emulsion used in the present invention, for example, the above-mentioned monodisperse emulsion may be cubic, octahedral or tetradecahedral, or spherical, tabular or the like. However, a twin twin crystal having an aspect ratio of 3 or more is preferably used.

The average grain size of the silver halide emulsion grains used in the present invention is preferably 0.1 to 5.0 μm, more preferably 0.15 to 3.0 μm, particularly preferably 0.2 to 2.0 μm.
μm.

Monodisperse emulsions are preferred because they have good graininess and, at the same time, have a sharpness of images in the size range where light scattering is small. Regarding the monodisperse emulsion, for example, JP-A-54-48521, JP-A-54-99419, JP-A-56-16124,
56-78831, U.S. Pat.No. 4,444,877, JP-A-57-1827
30, 58-49938, 58-37635, U.S. Pat.No. 4,446,
228, JP-A-58-106532, 58-107530, 58-1265
No. 31, No. 58-149037, No. 59-10947, No. 59-29243,
59-72440, 59-140443, 59-148049, 59-1
77535, 59-152438 and the like.

In the case of constituting the light-sensitive material of the present invention, the emulsion of the present invention to be used and other silver halide emulsions other than the emulsion of the present invention which are optionally used are generally preferably subjected to physical ripening and chemical ripening, In general, spectral sensitization is used depending on the photosensitive layer of each color used. Additives that can be used in such a process are exemplified in Research Disclosure No. 17643, No. 18716, and No. 308119 (hereinafter abbreviated as RD17643, RD18716, and RD308119, respectively).

The table below shows the locations.

Item RD308119 page RD17643 RD18716 and item page page Chemical sensitizer 996 III-A Item 23 648 Spectral sensitizer 996 IV-A-A, B 23-24 648-9 C, D, H , I, J item Supersensitizer 996 IV-A-E, J item 23-24 648-9 Antifoggant 998 VI 24-25 649 Stabilizer 998 VI 24-25 649 Also used in the practice of the present invention The known photographic additives that can be used are also exemplified in the above-mentioned Research Disclosure. Shown below are the relevant locations.

Item RD308119 page RD17643 RD18716 and item page page Color turbidity inhibitor 1002 VII-I Item 25 650 Dye image stabilizer 1002 VII-J Item 25 Whitening agent 998 V 24 UV absorber 1003 VIIIC, XIIIC Item 25-26 Light absorber 1003 VIII 25-26 Light scattering agent 1003 VIII Filter dye 1003 VIII 25-26 Binder 1003 IX 26 651 Antistatic agent 1006 XIII 27 650 Hardener 1004 X 26 651 Plasticizer 1006 XII 27 650 Lubrication Agent 1006 XII 27 650 Activator / Coating aid 1005 XI 26 to 27 650 Matting agent 1007 XVI Developer 1011 XXB (included in photosensitive material) In the photosensitive material of the present invention, the color to be developed in each color photosensitive layer A variety of couplers can be used depending on the type, specific examples of which are illustrated in Research Disclosure above. The following table shows the relevant locations.

Item Page of RD308119 RD17643 Yellow coupler 1001 VII-D item VII C to G item Magenta coupler 1001 VII-D item VII C to G item Cyan coupler 1001 VII-G item Colored coupler 1002 VII- Item G VII G Item DIR coupler 1001 VII-F item VII F item BAR coupler 1002 VII-F Other useful residue 1001 VII-F item releasing coupler Alkali-soluble coupler 1001 VII-E Various types of photosensitive materials of the present invention When additives are used, these can be added by the dispersion method described in RD308119XIV.

In the present invention, 28 of RD17643 described above is used.
Pages, pages 647-8 of RD18716, and X of RD308119
The supports described in VII can be used.

The light-sensitive material of the present invention includes the above-mentioned RD308119.
An auxiliary layer such as a filter layer or an intermediate layer described in the section VII-K can be provided.

The light-sensitive material of the present invention is the above-mentioned VI of RD308119.
Various layer configurations such as the forward layer, the reverse layer, and the unit configuration described in the section I-K can be adopted.

The present invention can be applied to various color light-sensitive materials represented by color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers. it can.

The light-sensitive material of the present invention is RD17643 28-29.
Page, page 615 of RD18716, and XIX of RD308119
The development processing can be carried out by a usual method described in the section.

[0089]

EXAMPLES The present invention will now be specifically described with reference to examples, but the present invention is not limited thereto.

Example 1 First, a method for preparing the emulsions Em-A and Em-B according to this example will be described below.

Preparation of Emulsion Em-A The method for preparing Emulsion Em-A will be described.

The following aqueous solutions (a-1) to (a-4) were used.

Aqueous solution (a-1) Gelatin 51.93 g 28% ammonia water 1056 ml 56% acetic acid 1590 ml Water is added to make 11827 ml.

Aqueous solution (a-2) AgNo ₃ 1587 g 28% ammonia water 1294 ml Water is added to make 2669 ml.

Aqueous solution (a-3) Gelatin 34.93 g KBr 1454.7 g Water is added to make 3493 ml.

Emulsion Solution Containing AgI Fine Particles (Average Particle Diameter 0.06 μm) (a-4) AgI Fine Particle Stock Solution [45.6 g gelatin / mol AgI included] [1467 ml / mol AgI] 1239 ml 4-hydroxy-6-methyl-1 2,3,3a, 7-Tetrazaindene 5.22g Add water to make 2294ml.

0.407 mol of a monodisperse silver iodobromide emulsion containing 2 mol% of silver iodide and having an average particle size of 0.27 μm was added to an aqueous solution (a-1) of the above composition which was vigorously stirred at a temperature of 60 ° C. The equivalent was added as seed particles and the pH and pAg were adjusted using acetic acid and aqueous KBr solution.

Thereafter, while controlling the pH and pAg as shown in Table 1, the aqueous solutions (a-2), (a-3) and (a-4) were simultaneously treated at the flow rates shown in Tables 2 and 3. Added by mixing method.

[0099]

[Table 1]

[0100]

[Table 2]

[0101]

[Table 3]

Then, a phenylcarbamyl gelatin solution was added to the above-obtained solution, and the pH of the solution was adjusted to precipitate and agglomerate the particles, followed by desalting and washing with water.

Thus, a monodisperse emulsion Em-A having an average grain size of 0.8 μm and an average silver iodide content of 8.0 mol% was obtained.

According to the measurement result by the powder X-ray diffraction method, Em-A
Was found to be an emulsion having a core with an AgI content of 35 mol%.

Preparation of Emulsion Em-B A method for preparing Emulsion Em-B will be described.

Emulsion Em-B consisting of tabular twin crystals was prepared by using a monodisperse twin seed emulsion having an average grain size of 0.36 μm and a broad distribution (variation coefficient) of 18% and the following five kinds of solutions. .

(B-1) Ocein gelatin 97 g Propyleneoxy-polyethyleneoxy-disuccinate disodium salt (10% methanol solution) 10 ml Seed emulsion 0.191 mol equivalent Water 400 ml (b-2) Silver nitrate 233 g Water 1662 ml (b-3) ) Ocein gelatin 83.1g Potassium bromide 131g Potassium iodide 45.5g Water 1662ml (b-4) Silver nitrate 934g Water 2749ml (b-5) Ocein gelatin 137g Potassium bromide 635g Potassium iodide 27.4g Water 2749ml 75 Solution (b-1) and solution (b-2) and (b-
3) The initial flow rate of 8.6 ml /
Min, accelerating addition such that the final flow rate was 25 ml / min and increased linearly with the addition time. At this time, pAg was kept at 8.5.

Subsequently, the liquid (b-4) and the liquid (b-5) were
The initial flow rate was 15 ml / min and the final flow rate was 34 ml / min, and accelerated addition was performed so as to increase linearly with the addition time. At this time pA
The g was kept at 9.0.

Solution (b-2), solution (b-3), solution (b-4),
The pH of the solution (b-5) was adjusted to 3.0 with nitric acid.
Kept at.

After the addition was completed, the pH was adjusted to 6.0 with an aqueous potassium hydroxide solution. In order to remove excess salts, precipitation desalting was carried out using a demol (Kao Atlas) aqueous solution and a magnesium sulfate aqueous solution to obtain an emulsion having a pH of 5.85 at pAg 8.5 and 40 ° C.

Observation of the obtained emulsion B under an electron microscope revealed that 75% of the total projected area was occupied by tabular grains, the average projected area grain size was 1.5 μm, and the average aspect ratio was 3.5.

Example-2 Emulsion A was adjusted to pAg8.0, and this emulsion was divided into two parts.
Each was subjected to different types of chemical sensitization. For one emulsion, 1.0 × 10 ^-4 mol / mol AgX of sodium thiosulfate was added instantaneously with the ripening temperature kept constant at 55 ° C. from the beginning to the end of ripening, followed by ripening for 60 minutes, and then chloroauric acid 2.2 × 10 ^-5 mol / mol A mixed solution of mol AgX and ammonium thiocyanate was added, and the mixture was further aged for 1 hour. This emulsion is designated as A-1.

In the other emulsion, the temperature was kept constant at 75 ° C. and the same amount of sodium thiosulfate as that used in Emulsion A-1 was used.
A constant flow rate was added during the minutes. Emulsion A-
The same amount of the mixed solution of chloroauric acid and ammonium thiocyanate used in 1 was added, and the aging was continued for another hour. The emulsion thus obtained is referred to as Emulsion A-2.

The emulsions A-1 and A-2 were observed by an electron microscope by the gelatin prepuce method, and photographs of them are shown in FIGS. 1 and 2.

Since Emulsion A is a monodisperse octahedral grain and sodium thiosulfate is a (111) face-selective sensitizer, the aggregate of gold and silver sulfide molecules produced is as shown in FIGS. 1 and 2. Although the particles are dispersed over the entire surface of the particle, as apparent from FIGS. 1 and 2, according to the present invention, the aggregate size of the gold / silver sulfide nucleus molecules is about twice as large as the circle-converted diameter in FIGS. 1 and 2. 2 shows the emulsion of the present invention, but the aggregate size of the molecules of the chemically sensitized nuclei is 2 or more, and the growth of the chemically sensitized nuclei is occurring as compared with the conventional example of FIG. I understand.

Example-3 Sodium thiosulfate of Example-2 was used as a thiourea compound.
Emulsion A by conventional chemical sensitization by the same method as in Example-2 except that 1-ethyl-3-amidino-2thiourea was used.
-3 and Emulsion A-4 according to the present invention were prepared and the same observation was performed.

The growth of gold and silver sulfide is (100) in the case of this compound.
Emulsion A-3, which is a surface-selective type and appears near the top of grains.
In comparison with the emulsion A-4, the gold-silver sulfide aggregate of the emulsion A-4 had a circle-equivalent average particle size of 2 times or more, and the compound constituting the chemical sensitizing nucleus was 2
It was shown to have aggregates that were aggregated over molecules.

Example-4 2.0 × 10 ^-6 mol / mol AgX of sodium thiosulfate was added instantaneously to Emulsion A, and the mixture was ripened at 60 ° C. for 60 minutes. Then, a mixed solution of 4.4 × 10 ⁻⁷ mol / mol AgX of chloroauric acid and ammonium thiocyanate was added, and the mixture was aged for 1 hour.

To this emulsion, the sensitizing dye SD-A shown below,
Spectral sensitization was performed by using B and C together. The emulsion obtained by such a conventional chemical sensitization method is referred to as Emulsion A-5.

[0120]

[Chemical 1]

Emulsion A was also prepared according to the present invention at 75 ° C. to 2.0 × 1.
0 ^-6 mol / mol AgX sodium thiosulfate was added at a constant flow rate over 60 minutes.

Then, a mixed solution of 4.4 × 10 ⁻⁷ mol / mol AgX of chloroauric acid and ammonium thiocyanate was added, and further,
After ripening for 60 minutes, spectral sensitization was performed in exactly the same manner as Emulsion A-5, and this emulsion was designated as Emulsion A-6.

Emulsion A-7 was prepared in the same manner as Emulsion A-6 except that the chemical ripening temperature was changed from 75 ° C to 55 ° C.

Further, magenta couplers MA, B and C were added to emulsions A-5, A-6 and A-7. Also, from the observation of the size of the chemically sensitized nuclei, Emulsions A-6 and A-7 were compound sizes of two or more molecules, and the average size was larger than that of Emulsion A-5.

[0125]

[Chemical 2]

Next, as a hardener, 2-hydroxy-4,6-
After uniformly adding an appropriate amount of sodium dichlorotriazine, each emulsion was coated on an undercoated triacetate support so that the coating silver amount was 2.0 g / m ² , and dried to give Sample Nos. 1 to 3. Obtained.

These various samples were wedge-exposed in the usual manner using green light, and color-developed according to the following color processing steps, and the photographic performances were compared and evaluated.

The results are shown in Table 4. The sensitivities in the table are expressed as relative sensitivities, where the sensitivity of comparative sample No. 1 is 100.

[0129]

[Table 4]

Sensitivity was defined as the reciprocal of the amount of exposure giving a fog density + 0.1.

As shown in Table 4, the emulsion samples of the present invention have higher photographic sensitivity and less fog than the emulsion samples used for comparison.

Treatment process Treatment temperature 38 ° C. Treatment time Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Water wash 3 minutes 15 seconds Settling 6 minutes 30 seconds Water wash 3 minutes 15 seconds Stabilization 1 minute 30 seconds Dry The composition of the processing solution used in each processing step is as follows.

(Color developer) 4-amino-3-methyl-N-ethyl-N-β-hydroxyethyl aniline sulfate 4.75 g anhydrous sodium sulfite 4.25 g hydroxylamine 1/2 sulfate 2.0 g anhydrous potassium carbonate 37.5 g Sodium bromide 1.3 g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Water is added to make 1 liter, and the pH is adjusted to 10.6 using sodium hydroxide.

(Bleach) Ethylenediaminetetraacetic acid ammonium salt 100.0 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 g Add water to make 1 liter, and adjust to pH 6.0 with aqueous ammonia. .

(Fixer) Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.6 g Sodium metasulfite 2.3 g Water is added to make 1 l, and pH is adjusted to 6.0 with acetic acid.

(Stabilizing Solution) Formalin (37% aqueous solution) 1.5 ml Conidax (manufactured by Konica Corporation) 7.5 ml Water is added to make 1 liter.

Example-5 Em-B prepared in Example-1 was pAg8.5.
Was adjusted to 7 and divided into 7, and then chemically and spectrally sensitized as follows.

These emulsions are respectively emulsions B-1 to B-
7

(Emulsion B-1) The temperature of the emulsion was adjusted to 60 ° C., 1.3 × 10 ^-6 mol / mol of AgX sodium thiosulfate was added instantaneously, and the mixture was aged for 60 minutes, and then chloroauric acid 2.8 × 10 5. ^-7
A mixture of mol / mol AgX and ammonium thiocyanate was added, and the mixture was aged for 60 minutes. Emulsion B-1 is a conventional emulsion obtained by spectrally sensitizing this emulsion in combination with SD-6, 7 and 8 shown below.

[0140]

[Chemical 3]

(Emulsion B-2) The temperature of the emulsion was adjusted to 75 ° C., and 1.3 × 10 ⁻⁶ mol / mol of AgX of sodium thiosulfate was added to 60.
Add chlorauric acid 2.8 after the addition at a constant flow rate over a period of time
A mixed solution of × 10 ^-7 mol / mol AgX and ammonium thiocyanate was added, and the mixture was aged for 60 minutes. Then emulsion B-
Spectral sensitization was performed as in 1. This emulsion of the present invention is designated as B-2.

(Emulsion B-3) The type and amount of the sensitizing dye were exactly the same as those in Emulsion B-2, and sodium thiosulfate was added for 60 minutes only at the position where the sensitizing dye was added. Emulsion B-3 was prepared in the same manner as Emulsion B-2, except that it was added before the addition.

(Emulsion B-4) Except for the fact that sodium thiosulfate is not added at a constant flow rate but addition is completed in 60 minutes by a quadratic function with respect to time, the types and addition amounts of other additives are the same.
Emulsion B-4 was prepared in exactly the same manner as in 3.

(Emulsion B-5) Sensitizing dyes SD-6,7,8 were added in exactly the same manner as in Emulsion B-3, and after adsorbing for 10 minutes, 10% of the total amount of sodium thiosulfate was instantaneously added. The remaining sodium thiosulfate at a constant flow rate for another 20 minutes.
Added for 60 minutes.

Thereafter, chloroauric acid and ammonium thiocyanate were added in the same manner as in Emulsion B-4.
-5.

(Emulsion B-6) An emulsion prepared in exactly the same manner as Emulsion B-3 except that sodium thiosulfate was replaced with triethylthiourea was designated as B-6.

(Emulsion B-7) An emulsion prepared in the same manner as Emulsion B-3 except that potassium hexacyanoferrate (II) was added and then sodium thiosulfate was added to coexist with both emulsions. 7

Furthermore, magenta coupler M was added to these emulsions.
-1, M-3 and CM-1 were added and used as an emulsion for constituting the ninth layer of the color multilayer light-sensitive material shown below. The above emulsion was used to form the ninth layer, and a multilayer sample N
o.101-107 were prepared.

The structure of the basic multilayer sample No. 101 is shown below.

In all the following descriptions, the amount of the compound added to the AgX photographic light-sensitive material is 1 m unless otherwise specified.
^The number of grams per ² is shown.

Further, AgX and colloidal silver are shown in terms of silver, and the addition amount of the sensitizing dye is shown by the number of moles per 1 mole of AgX in the same layer.

Sample-101 First Layer; Antihalation Layer (HC-1) Black Colloidal Silver 0.2 UV Absorber (UV-1) 0.23 High Boiling Solvent (Oil-1: Dioctylphthalate) 0.18 Gelatin 1.4 Second Layer; Intermediate Layer (IL-1) Gelatin 1.3 Third layer; Low-sensitivity red-sensitive emulsion layer (RL) Silver iodobromide emulsion (grain size 0.40 μm, average AgI content 8.0 mol%) 1.0 Sensitizing dye (SD-1) 1.8 × 10 ^-5 Sensitizing dye (SD-2) 2.8 × 10 ^-4 Sensitizing dye (SD-3) 3.0 × 10 ^-4 Cyan coupler (C-1) 0.70 Colored cyan coupler (CC-1) 0.066 DIR compound ( D-1) 0.03 DIR compound (D-3) 0.01 High boiling point solvent (Oil-1) 0.64 Gelatin 1.2 Fourth layer; Medium speed red-sensitive emulsion layer (RM) Silver iodobromide emulsion (grain size 0.7 μm, average AgI) Content 8.0 mol%) 0.8 Sensitizing dye (SD-1) 2.1 × 10 ^-5 Sensitizing dye (SD-2) 1.9 × 10 ^-4 Sensitizing dye (SD-3) 1.9 × 10 ^-4 Cyan coupler (C-1) 0.28 Colored cyan coupler (CC-1) 0.027 DIR compound (D-1) 0.01 High boiling point solvent (Oil-1) 0.26 Gelatin 0.6 Fifth layer; High-sensitivity red-sensitive emulsion layer (RH) Silver iodobromide emulsion (Em-B-1) 1.70 Sensitizing dye (SD-1) 1.9 × 10 ^-5 Sensitizing dye (SD-2) 1.7 × 10 ^-4 Sensitizing dye (SD-3) 1.7 × 10 ^-4 Cyan coupler (C-1) 0.05 Cyan coupler (C-2) 0.10 Colored cyan coupler (CC-1) 0.02 DIR compound (D-1) 0.025 High boiling point solvent (Oil-1) 0.17 Gelatin 1.2 No. 6 layers; intermediate layer (IL-2) gelatin 0.8 7th layer; low-sensitivity green sensitive emulsion layer (GL) silver iodobromide emulsion (grain size 0.4 μm, average AgI content 8.0 mol%) 1.1 sensitizing dye (SD ─4) 6.8 × 10 ^-5 sensitizing dye (SD─5) 6.2 × 10 ^-4 magenta coupler (M─1) 0.54 magenta coupler (M-2) 0.19 colored magenta coupler (CM-1) 0.06 DIR compound (D-2) 0.017 DIR compound (D-3) 0.01 High boiling point solvent (Oil-2: tricresyl phosphate) 0.81 Gelatin 1.8 Eighth layer; Medium sensitivity green sensitive emulsion layer (GM) ) Silver iodobromide emulsion (grain size 0.7 μm, average AgI content 8.0 mol%) 0.7 sensitizing dye (SD-6) 1.9 × 10 ^-4 sensitizing dye (SD-7) 1.2 × 10 ^-4 sensitizing dye (SD-8) 1.5 × 10 ^-5 Magenta coupler (M-1) 0.07 Magenta coupler (M-2) 0.03 Colored magenta coupler (CM-1) 0.04 DIR compound (D-2) 0.018 High boiling point solvent (Oil-2) ) 0.30 gelatin 0.8 9th layer; high sensitivity green sensitive emulsion layer (GH) silver iodobromide emulsion (Em-B-1) 1.7 sensitizing dye (SD-6) 1.2 × 10 ^-4 sensitizing dye (SD-7) ) 1.0 × 10 ^-4 Sensitizing dye (SD-8) 3.4 × 10 ^-6 Magenta coupler (M-1) 0.09 Magenta coupler (M-3) 0.04 Colored magenta coupler (CM-- 1) 0.04 High boiling point solvent (Oil-2) 0.31 Gelatin 1.2 10th layer; Yellow filter layer (YC) Yellow colloidal silver 0.05 Color contamination inhibitor (SC-1) 0.1 High boiling point solvent (Oil-2) 0.13 Gelatin 0.7 Formalin Scavenger (HS-1: 5-ureidohydantoin) 0.09 Formalin scavenger (HS-2: hydantoin) 0.07 11th layer; low-sensitivity blue-sensitive emulsion layer (BL) Silver iodobromide emulsion (grain size 0.4 μm, average AgI content) 8.0 mol%) 0.5 silver iodobromide emulsion (particle size 0.7 [mu] m, an average AgI content of 8.0 mol%) 0.5 sensitizing dye (SD-9) 5.2 × 10 -4 sensitizing dye (SD-10) 1.9 × 10 - ⁵ Yellow coupler (Y-1) 0.65 Yellow coupler (Y-2) 0.24 DIR compound (D-1) 0.03 High boiling point solvent (Oil-2) 0.18 Gelatin 1.3 Formalin scavenger (HS-1) 0.08 12th layer; high sensitivity Blue-sensitive emulsion layer (BH) Silver iodobromide emulsion (Em-B-1) 1.0 Sensitizing dye (SD-9) 1.8 × 10 ^-4 Sensitizing dye (SD-10) 7.9 × 10 ^-5 Yellow coupler (Y-1) 0.15 Yellow coupler (Y-2) 0.05 High boiling point solvent (Oil-2) 0.074 Gelatin 1.3 Formalin scavenger (HS-1) 0.05 Formalin scavenger (HS-2) 0.12 13th layer; 1st protective layer (Pro-1) Fine grain silver iodobromide emulsion 0.4 (Average grain size 0.08 μm Average AgI content 1 UV absorber (UV-1) 0.07 UV absorber (UV-2) 0.10 High boiling point solvent (Oil-1) 0.07 High boiling point solvent (Oil-3: dibutyl phthalate) 0.07 Formalin scavenger (HS-1) 0.13 Formalin scavenger (HS-2) 0.37 Gelatin 1.3 14th layer; Second protective layer (Pro-2) Alkali-soluble matting agent (average particle size 2 μm) 0.13 Polymethylmethacrylate (average particle size 3 μm) 0.02 Sliding agent (WAX-1) ) 0.04 The compounds that were used in the keratin 0.6 sample No.101~107 below.

[0153]

[Chemical 4]

[0154]

[Chemical 5]

[0155]

[Chemical 6]

[0156]

[Chemical 7]

[0157]

[Chemical 8]

[0158]

[Chemical 9]

[0159]

[Chemical 10]

In addition to the above composition, coating aid sodium dioctylsulfosuccinate, dispersion aid sodium-tri (isopropyl) naphthalene sulfonate, viscosity modifier, hardener 2,4-dichloro-6-hydroxy- s-Triazine sodium salt, di (vinylsulfonylmethyl) ether, stabilizer 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, antifoggant 1-phenyl-5-mercaptotetrazole, weight average Two types of poly with molecular weights of 10,000 and 1,100,000
N-vinylpyrrolidone was added.

The above sample Nos. 101 to 107 were subjected to wedge exposure through a yellow filter and then subjected to the following developing treatment.

Processing step (38 ° C.) Color development Standard 2 minutes 45 seconds Bleach 6 minutes 30 seconds Water washing 3 minutes 15 seconds Settling 6 minutes 30 seconds Water washing 3 minutes 15 seconds Stabilization 1 minute 30 seconds Dry each The composition of the processing liquid used in the processing step is as follows.

(Color developer) 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline / sulfate 4.75 g anhydrous sodium sulfite 4.25 g hydroxylamine / 1/2 sulfate 2.0 g anhydrous Potassium carbonate 37.5g Sodium bromide 1.3g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5g Potassium hydroxide 1.0g Add water to make 1 liter (pH = 10.1) (bleaching solution) Ethylenediaminetetraacetic acid iron (III) ) Ammonium salt 100.0 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 g Add water to make 1 liter, and adjust to pH 6.0 with aqueous ammonia.

(Fixer) Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Water is added to make 1 l, and the pH is adjusted to 6.0 with acetic acid. (Stabilizer) Formalin (37% aqueous solution) 1.5 ml Conidax (Konica Corporation) 7.5 ml Add water to make 1 liter. The relative sensitivity of each of the obtained samples was measured using green light. The results at that time are shown in Table 5.

Sensitivity was defined as in Example 4, and sample N
The sensitivity of o.101 after one day of standing naturally was defined as 100, and the relative sensitivity was shown.

[0166]

[Table 5]

As can be seen from the results of Sample Nos. 101 and 102 in Table 5, when the chemical sensitization method of the present invention is used, the size of the aggregate of compound molecules constituting the chemical sensitization nucleus is increased, and both sensitivity and fog are increased. It can be seen that it will be greatly improved. In addition, Sample No. 103 to 107, which is a combination of the method of Sample 102 of the present invention and a method of increasing the number of molecules of the compound forming the chemical sensitization nucleus (growing the chemical sensitization nucleus), has further improved sensitivity. It was observed.

Sample No. 106 using a specific thiourea compound that forms silver sulfide only on the (100) plane, not only on the size of the aggregate of compound molecules constituting the chemically sensitized nucleus,
Is preferable in terms of sensitivity and fog because not only the growth of chemically sensitized nuclei occurs but also the growth at selective sites on the grain surface occurs.

Sample No. 107, to which potassium hexacyanoferrate (II) was added at the beginning of chemical ripening, had the largest sensitizing effect. Further, although not shown in Table 5, instead of potassium hexacyanoferrate (II) used in Emulsion B-7,
NN ′ dimethylselenourea 1.3 × 10 ^-7 mol / mol AgX
The same effects as those of the present invention were exhibited when an emulsion was prepared in exactly the same manner as Emulsion B-6 except that it was added.

[0170]

INDUSTRIAL APPLICABILITY According to the present invention, a silver halide emulsion having high sensitivity and less fog can be obtained by controlling the size of the chemically sensitized nuclei. The fog has been greatly improved.

[Brief description of drawings]

FIG. 1 is a silver halide emulsion A- shown in Example 2.
1 is a photograph of the grain structure of chemically sensitized nuclei taken with an electron microscope (40,000 times).

FIG. 2 is a grain structure photograph (40,000 times) of a chemically sensitized nucleus of the silver halide emulsion A-2 according to the present invention obtained in Example 2, taken by an electron microscope.

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[Procedure amendment]

[Submission date] July 23, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Brief description of the drawing

[Correction method] Delete

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Claims (9)

[Claims] 1. The chemically sensitized nuclei formed on the photosensitive silver halide grains are sulfur, selenium, tellurium, and Periodic Table VI.
II An aggregate composed of two or more compound molecules containing at least one atom selected from noble metals, and the amount of the compound molecules is 1 × 10 ^-4 per mol of silver halide.
A silver halide photographic emulsion characterized in that it is at most a molar amount. 2. The silver halide photograph according to claim 1, wherein at least one selected from a thiourea compound, a selenourea compound, and a dithiacarbamic acid compound is used as the chemical sensitizer. emulsion. 3. The method for producing a silver halide photographic emulsion according to claim 1, wherein the chemical sensitizer is added in a plurality of divided portions or continuously. 4. The production of a silver halide photographic emulsion according to claim 1, wherein a chemical sensitizer is added under a temperature condition of 50 ° C. or higher, and a high temperature of 70 ° C. or higher is passed during ripening. Method. 5. A thiocyanate compound, a thioether,
2. The method for producing a silver halide photographic emulsion according to claim 1, wherein the chemical ripening is carried out in the presence of at least one selected from the group consisting of and a telluroether. 6. The method for producing a silver halide photographic emulsion according to claim 1, wherein the chemical ripening is carried out in the presence of a heterocyclic compound having an azaindene or a mercapto group. 7. The grains are composed of (111) planes and (100) planes, and the chemical sensitization nuclei are formed on the narrow planes of the grains in which the ratio of one plane to the whole plane is 40% or less. The method for producing a silver halide photographic emulsion according to claim 1, wherein the silver halide photographic emulsion is formed. 8. A lattice defect or at least one of a silver sulfide nucleus, a gold nucleus, a gold sulfide silver nucleus and a silver nucleus is formed in advance in the vicinity of a ridgeline or a vertex of a silver halide grain, and then a chemical sensitizer is added. The method for producing a silver halide photographic emulsion according to claim 1, wherein 9. The method for producing a silver halide photographic emulsion according to claim 1, wherein chemically sensitized nuclei are formed in advance and then the chemically sensitized nuclei are added to the emulsion.