JPS61245151A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To ensure high sensitivity, wide exposure latitude and superior graininess and sharpness by forming plural outer shells composed of silver halide grains (AgX) of specified compositions on an inner shell composed of silver bromide and/or silver iodobromide to prepare each negative type silver halide grain. CONSTITUTION:Each negative type silver halide grain is prepared by forming the plural outer shells composed substantially of silver bromide and/or silver iodobromide on the inner shell composed substantially of silver bromide and/or silver iodobromide and the silver iodide content of the outermost shell of this silver halide grain is regulated to <=10mol%, expressed in terms of iodin and the shell incorporating high contents of iodine to which the contents expressed in terms of iodin in outermost shell is controlled to >=6mol% is provided a the inside of the outermost shell and that of the intermediate layer between them is made higher than that of the outermost layer by >=3mol%, thus permitting such core-shell type silver halide grain having the inside shell higher in silver iodide content to be high in sensitivity, wide in exposure latitude, superior in graininess and the relationship between fog an sensitivity to be improved by forming the difference in the silver iodide content in the outer shells.

Description

DETAILED DESCRIPTION OF THE INVENTION A. Field of Industrial Application The present invention provides an internal core consisting essentially of silver bromide and/or silver iodobromide, and an internal core provided outside the internal core and consisting essentially of silver bromide and/or silver iodobromide. The present invention relates to a silver halide photographic light-sensitive material containing negative-working silver halide grains having a plurality of outer shells made of silver oxide and/or silver iodobromide.

2. Prior Art In recent years, demands for silver halide emulsions for photography have become increasingly strict, and even higher demands are being made for photographic performance such as high sensitivity, excellent graininess, high sharpness, low fog density, and a sufficiently wide exposure range. There are demands for standards.

In order to meet these demands, silver iodobromide emulsions containing 0 to 10 mol % of iodine are well known as high-sensitivity emulsions. Conventionally, methods for preparing these emulsions include pH conditions such as ammonia method, neutral method, and acidic method.
As a method of controlling Ag conditions and a mixing method, a single jet method, a double jet method, etc. are known.

Based on these known techniques, technical means have been elaborately studied and put into practical use for the purpose of achieving higher sensitivity, improved graininess, higher sharpness, and lower fog. Regarding the silver iodobromide emulsions targeted by the present invention, research has been conducted on emulsions in which not only the crystal habit and grain size distribution but also the iodine concentration distribution within each silver halide grain is controlled.

The most traditional method for achieving photographic performance such as high sensitivity, excellent graininess, high sharpness, and low fog density as described above is to improve the quantum efficiency of silver halide. For this purpose, personal opinions on solid state physics are actively incorporated.

A study that theoretically calculated this quantum efficiency and considered the influence of particle size distribution was described, for example, in the Proceedings of the 1980 Tokyo Symposium on Advances in Photography, "Interactions Between Light and Materials," page 91. has been done. According to this research, it is predicted that creating a monodisperse emulsion by narrowing the particle size distribution will be effective in improving quantum efficiency. In addition, in order to achieve sensitization of silver halide emulsions, monodisperse is used to efficiently achieve high sensitivity while maintaining low fog in a process called chemical sensitization, which will be described in detail later. It seems reasonable to infer that emulsions would be advantageous.

In order to industrially produce monodispersed emulsions, Japanese Patent Application Laid-Open No. 54-4
As described in Publication No. 8521, strict pAg
It is necessary to control the supply rate of silver ions and halogen ions that are theoretically hydrated to the reaction system under the control of pH and pH, and to have sufficient stirring conditions. Silver halide emulsions produced under these conditions have cubic, octahedral and 1
It has any shape of a tetrahedron, i.e. (100)
It consists of so-called normal crystal grains having various ratios of planes and (111) planes. It is known that such normal crystal particles can increase sensitivity.

On the other hand, silver iodobromide emulsions comprising polydisperse twin grains have been known as silver halide emulsions suitable for high-speed photographic films.

Further, silver iodobromide emulsions containing tabular twin grains are disclosed in JP-A-58-113927 and others.

On the other hand, in JP-A-53-2240, it was reported that developing activity could be increased and sensitivity could be increased by using laminated silver halide grains in which a plurality of shells were placed on the outside of an inner core.
Publication No. 8, Special Publication No. 43-13162, J, P
Hoto, Sct., 24.198 (1976), etc.

In addition, silver halide grains in which a coating layer is provided as the outermost layer of silver halide grains by halogen substitution are disclosed in West German Patent No.
No. 932650, Japanese Patent Application Laid-open No. 51-2417, 51
Although these silver halide grains may speed up the fixing speed, they also inhibit development and prevent sufficient sensitivity from being obtained. It cannot be used as a practical negative emulsion due to the lack of such characteristics.

In addition, positive type (internal latent image type) silver halide grains having a plurality of coating layers on the outside of the inner core by halogen substitution are known, and are disclosed in U.S. Pat. No. 2,592.250 and U.S. Pat. Specification No. 020, JP-A-55-12754
It is described in detail in Publication No. 9, etc. These silver halide grains are often used in internal latent image type direct positive light-sensitive materials such as those for diffusion transfer, and because of their high internal sensitivity, they cannot be used in the negative-tone emulsion that is the object of the present invention. 1 On the other hand, JP-A-58-181037 and JP-A-60-35
No. 726, JP-A-59-116647, and other publications also disclose silver halide grains having an outer shell on an inner core as described above, and in which the iodine content of each layer is taken into consideration in various ways. .

In the field of silver halide photographic materials, advances in various technologies have recently led to the appearance of color sensitive materials with an ISO sensitivity of over 1000. However, as the sensitivity of these photosensitive materials increases, their graininess and sharpness usually deteriorate, resulting in insufficient image quality compared to conventional photosensitive materials, making them extremely difficult for consumers to use for viewing purposes. The present situation is unsatisfactory, and a high-sensitivity negative light-sensitive material with excellent graininess and sharpness is desired.

Negative photosensitive materials with even higher sensitivity are required for astrophotography, indoor photography, sports photography, and the like.

The purpose of the present invention is to provide high sensitivity and excellent sensitivity-capri relationship.
The present invention provides a negative silver halide photographic material with a wide exposure range and excellent graininess and sharpness.

20 Structure of the invention and its effects, that is, the present invention comprises an inner core consisting essentially of silver bromide and/or silver iodobromide, and an inner core provided outside the inner core and consisting essentially of silver bromide and/or silver iodobromide. /or a silver halide photographic material containing negative-working silver halide grains having a plurality of outer shells made of silver iodobromide, wherein the iodine content of the outermost shell of the silver halide grains is 10 mol% or less and an iodine-rich shell (hereinafter referred to as
a high-iodity shell) is provided inside the outermost shell,
An intermediate shell having an iodine content between these 100 types is provided between the outermost shell and the high iodine content shell, and the iodine content of the intermediate shell is 3 mol% or more higher than that of the outermost shell. , the iodine content of the iodine-rich shell is 3% higher than that of the intermediate shell.
This invention relates to a silver halide photographic light-sensitive material characterized by a high mole % or more.

In the silver halide composition of the silver halide grains according to the present invention, the above-mentioned "consisting essentially of" means silver bromide or iodine to the extent that the effects of the present invention are not impaired. This means that silver halide other than silver bromide, such as silver chloride, may be contained. Specifically, in the case of silver chloride, the proportion thereof is preferably 1 mol % or less.

To summarize the features of the photographic material according to the present invention,
As shown in (1) to (7) below.

(1) By using an emulsion containing core/shell type silver halide grains with a high iodine shell on the inside, high sensitivity, wide exposure range, and excellent graininess can be achieved (compared to non-core/shell emulsions). can get.

(2) Even higher sensitivity can be obtained by providing an intermediate shell having an intermediate iodine content between the high iodine shell and the low iodine shell (outermost shell layer) on the surface.

(3) The iodine content of the high iodine shell is preferably 6 to 40 mol%, and is 6 mol% or more higher than the outermost shell layer, but if this content is less than 6 mol%, or the iodine content is higher than the outermost shell layer. If the amount is less than 6 mol %, the sensitivity will decrease, and if it exceeds 40 mol %, polydispersity will occur. Therefore, from the viewpoint of sensitivity and sharpness, it is preferable not to exceed 40 mol %.

(4) The difference in iodine content between the middle shell and the outermost shell or high iodine shell should be 3 mol% or more, but this is because if this difference is too small, the effect of the middle shell will be reduced. This is because the sensitivity decreases (sensitivity decreases). Further, it is desirable that the upper limit of this difference in iodine content is 35 mol % from the viewpoint of effectively bringing out the effects of the intermediate shell (sensitivity, monodispersity, Capri-sensitivity relationship, sharpness).

(5) If the iodine content in the entire silver halide grain is too high, developability will be poor and sensitivity will be lowered; if it is too low, the gradation will be too hard, the exposure area will be narrow, and grain Therefore, it is preferable to select a specific range.

(6) Monodisperse emulsions are better in sensitivity, sharpness, and fog-sensitivity relationships than polydisperse emulsions. In other words, in polydispersion, the shell-forming reaction is non-uniform, making it difficult to form an ideal core/shell structure, the presence of microparticles that degrade sharpness, and chemical sensitization after particle formation. Since the optimum conditions differ depending on the individual grains, the sensitivity tends to be low and the fog-sensitivity relationship tends to deteriorate, so monodisperse emulsions are preferably used.

(7) In multilayer color light-sensitive materials, a phenomenon occurs in which sensitivity deteriorates compared to a single layer due to multilayering (referred to as multilayer desensitization effect), but the emulsion of the present invention
Not only does it have high sensitivity as a single layer, but it is also less susceptible to this multilayer desensitization effect, so it can be used more effectively in multilayer color light-sensitive materials.

In order to further improve the above-mentioned excellent effects, ■h: Iodine content of high iodine shell (mol%) 1 m: Iodine content of intermediate shell (mol%) IL: Iodine content of outermost shell (mol%) %)
When, ΔI = T h IL > 8 mol%,
Δ■1=■ゎ−■, 〉4 mol%, ΔIA=1. -Iz＞
It is better to set it to 4 mol%, ΔIz>10 mol%, Δlh
>4 mol%, Δ■t>4 mol% is even better (
(4) above). Here, it is preferable that It=O to 5 mol%, preferably 0 to 2 mol%, and more preferably 0 to 1 mol%. Also, ■, is 6 to 40 mol% <, 10 to 4
Even better is 0 mol% ((3) above).

In addition, the volume of the outermost shell is 4 to 70 mol% of the entire particle.
, 10 to 50 mol% is more preferable. The volume of the high iodine shell is preferably 10 to 80% of the whole grain, and 20 to 80% of the total grain.
50%, more preferably 20-45%. The volume of the intermediate shell is preferably 5 to 60%, more preferably 20 to 55%, of the entire particle. The high-iodity shell may be at least part of the inner shell,
Preferably, a separate internal core exists inside the high iodine shell.

The iodine content of the internal core is preferably 0 to 40 mol%, and 0 to 10
Mol% is preferred, and 0 to 6 mol% is more preferred. The particle size of the inner core is 0.05 to 0.8 μm, and even 0.05 to 0.
．． 4 μm is good.

In addition, in the characteristic point (5) above, the iodine content in the entire particle is preferably 1 to 20 mol%, preferably 1 to 1 mol%.
The content is desirably 5 mol%, more preferably 2 to 12 mol%.

Regarding the characteristic point (6) above, the particle size distribution of the particles may be either polydisperse or monodisperse, but it is preferable that the coefficient of variation of the particle size distribution be a monodisperse emulsion of 20% or less; It is preferable that the coefficient of variation be 15% or less. This coefficient of variation is defined as , and is a measure of monodispersity.

As a multilayer color light-sensitive material according to the characteristic point (7) above, the multilayer is composed of three or more emulsion layers consisting of three types of light-sensitive layers: a blue-sensitive layer, a red-sensitive layer, and a green-sensitive layer, and at least one layer is composed of three or more emulsion layers. It is desirable that the emulsion layer contains silver halide grains according to the present invention (or preferred as described above).

The grain size of the silver halide grains (defined as the length of one side of a cube having the same volume as the silver halide grains) is 0.1 to 3.0.
It is preferable to set it to μm. Moreover, the shape may be any of an octahedron, a cube, a sphere, a flat plate, etc., but an octahedron is preferable.

To further describe the layer structure of the silver halide grains of the present invention, as described above, the inner core and the high iodine shell may be the same, or the inner core may be provided separately inside the high iodine shell. It's okay. The inner core and the high iodine shell, the high iodine shell and the middle shell, and the middle shell and the outermost shell may be adjacent to each other, or there may be at least one layer of another shell having an arbitrary composition between each shell. (This is called an arbitrary shell).

These arbitrary shells may be a single shell with a uniform composition, a group of shells whose composition changes stepwise, consisting of multiple shells with a uniform composition, or continuous shells within an arbitrary shell. It may be a continuous shell whose composition changes over time, or it may be a combination of these. Further, there may be a plurality of high-iodity shells and intermediate shells, or there may be only one set.

Next, an example of the layer structure of silver halide grains according to the present invention will be explained. The iodine content is indicated by I.

1. Inner core = 3N structure iodine content of high iodine shell Shell diameter core (third) (inner core = high iodine shell) I3-I, >3 mol% 13-15 mol% 1.2 μm
2nd shell (middle shell) I, -I, >3 mol% 5 mol% in I2 1.4 μm 1st shell (outermost shell) I+=o ~10 mol% I+=0.5 mol% 1.6
．． crm2, a fourth of arbitrary composition between the inner core and the high-iodide shell
, 6-layer structure including 5th shell Iodine content Shell diameter core (6th) (inner core) Arbitrary 1b"4.0 mol% o, iμ
m 5th shell (-) Arbitrary 1 s = 2.0 mol% 0
．． 27. izm 4th shell (-) Arbitrary 14=2.6 mol% 0.8μ
m 3rd shell (high iodine shell) Iff 12>3 mol% l1=15.0 mol%
1.12 μm second shell (intermediate shell) Iz It>3 mol% l2=5.0 mol% 1.
44 μm first shell (outermost shell) 1, = 0 to 10 mol% ■, = 0.5 mol% 1.6
Layer m3゜ An arbitrary 5th layer between the inner shell and the high iodine shell. 6th shell,
and 7-layer structure with two intermediate shells between the outermost shell and the high iodine shell Iodine content Shell diameter 7th shell (inner core) ■7=47=4 0.10um 6th shell (optional insertion Shell) Any ■6=26=2 0.27μm
5th shell (optional inserted shell) Optional I, Ki 8 mol% 0.8 μm
4th shell (high iodine shell) 14 13>3 mol% l4=15 mol% 1゜1
2μm third shell (intermediate shell) I3-It >3 mol% l3=8 mol% 1.24
μm14-I3 >3 mol% 2nd shell (middle shell) 1st shell (outermost shell) 1,=O~10 mol% 1. =0.5 mol% 1.6
Layer m4, any 6th and 7th shells between the inner shell and the high iodine shell,
and one layer of arbitrary shell (fourth shell) between the high-iodity shell (fifth shell) and the middle shell (third shell), and one layer of arbitrary shell (fourth shell) between the middle shell (third shell) and the outermost shell. 8-layer structure with arbitrary shell (second shell) Iodine content Shell diameter 8th shell (inner core) Arbitrary ■8=48=4 0.10μm
7th shell (arbitrary shell) Arbitrary ■7=27=2 0.27μm
6th shell (arbitrary shell) Arbitrary ■6=46=4 0.8μm 5th shell (high iodine shell) Is-13>3 mol% l5=15 mol% 1.12
μm 4th shell (arbitrary shell) Arbitrary l4=9 mol% 1.24u
m Third shell (middle shell) 13 11 = 3 mol% ■3=53=5 1.44
μm 2nd shell (arbitrary shell) Arbitrary Iz=4.5 mol% 1.50
μm first shell (outermost shell) ■, = O ~ 10 mol% l1 = 2 mol 9A1.6. u
m5, structural iodine content with multiple high iodine shells Shell diameter 6th shell (inner core) Arbitrary l6 = 4 mol% 0.10.
crm 5th shell (high iodine shell) Is rz>3 mol% Is''15 mol% 0.
27 p mts -II >6 mol% 4th shell (arbitrary shell) Arbitrary l4=5 mol% 0.80μ
m third shell (high iodine shell) 1, l I2>3 mol% l3=15 mol% 1.
12. crmI3 11>6 mol% Second shell (intermediate shell) I2-It >3 mol% ■2=52=5 1.44
μm 1st shell (outermost shell) ■1 = 0 to 10 mol% II = 0.3 mol% 1.6
The inner core of the 0 μm silver halide grain of the present invention is described by Glafkides, P., Chin+ie et P.
hysique, Photohraphique) (
Published by Paul Montel, 19
1967), G.F. Duff
in) Author: Photographic Emulsion Ch.
imistry) (The Focal Press (Th
e Focal Press, 1966), V. L. Zelikman et al., Making and Coating Photographic Illusions (1966)
ng Photographic Emulsion)
(The Focal Press
ess), 1964). That is, acidic method, neutral method,
Any method such as the ammonia method may be used, and methods for reacting soluble root salts with soluble halogen salts include one-sided mixing method,
Either a simultaneous mixing method or a combination thereof may be used.

It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).

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

Although two or more silver halide emulsions formed separately may be used as a mixture, it is preferable to use the double jet method or the controlled double jet method.

The pAg when preparing the inner core varies depending on the reaction temperature and the type of silver halide solvent, but is preferably 2 to 11. Further, it is preferable to use a silver halide solvent because the grain formation time can be shortened. For example, commonly known silver halide solvents such as ammonia and thioether can be used.

The shape of the internal core may be plate-shaped, spherical, twinned, or octahedral, cubic, tetradecahedral, or mixed.

Also, to make the particle size uniform, British patent 1.53
No. 5,016, Special Publication No. 48-36890, No. 52-1
As described in No. 6364, there is a method of changing the addition rate of silver nitrate or aqueous alkali halide solution depending on the grain growth rate, and as described in U.S. Pat. It is preferable to use a method of changing the aqueous solution concentration as described above to grow quickly within a range that does not exceed the critical saturation level.

These methods do not cause re-nucleation and each silver halide grain is uniformly coated, so arbitrary shells, high iodine shells,
It is also preferably used when introducing an intermediate shell or an outermost shell.

What about the silver halide grains of the present invention? ! After a desalting step is applied to the internal shell provided with the high iodine core or arbitrary shell, if necessary, the crystal can be provided by a conventional halogen substitution method, a method of coating with silver halide, or the like.

The halogen substitution method can be carried out, for example, by adding an aqueous solution consisting mainly of an iodo compound (preferably potassium iodo), preferably at a concentration of 10% or less, after the internal core is formed. For details, see U.S. Patent No. 2,592,250, No. 4,0
This can be carried out by the methods described in Japanese Patent Application Laid-open No. 75,020, Japanese Patent Application Laid-Open No. 55-127549, and the like.

At this time, in order to reduce the difference in iodine distribution between particles of the high iodine shell, it is desirable to add the iodine compound aqueous solution over a period of 10 minutes or more at a concentration of 10@-2 mol % or less.

Further, as a method for newly coating the inner core with silver halide, it can be carried out, for example, by simultaneously adding an aqueous halide solution and an aqueous silver nitrate solution, that is, by a simultaneous mixing method or a controlled double jet method. For details, see Japanese Patent Application Laid-open No. 53-22408, Japanese Patent Publication No. 43-1
No. 3162, JP-A-58-14829, J Photo Science (J, Photo.

Sci., 24, 198 (1976).

pAg when forming a high iodine shell is the reaction temperature,
Although it varies depending on the type and amount of the halogenated W and the solvent, those mentioned above are preferably used. When using ammonia as a solvent, 7 to 11 are preferable.

As a method for forming a high iodine shell, a simultaneous mixing method or a controlled double jet method is more preferable.

The intermediate shell of the silver halide grains of the present invention includes a high-iodide shell having a high-iodide shell on the surface, or a high-iodide shell having one or more arbitrary shells on the high-iodide shell as necessary, and an inner core. The outer surface of the grains containing iodine can be further coated with silver halide having a halogen composition different from that of the high iodine shell by a simultaneous mixing method or a controlled double jet method.

Regarding these methods, the method of providing a high iodine shell described above is similarly used.

The outermost shell of the silver halide grains of the present invention includes an intermediate shell, a high iodine shell, and an inner shell having an intermediate shell on the surface or having one or more arbitrary shells on the intermediate shell as necessary. Silver halide having a halogen composition different from that of the high iodine shell can be coated on the outside of the grains by a simultaneous mixing method or a controlled double jet method.

Regarding these methods, the above-mentioned method of providing a high iodine shell is similarly used.

One or more optional shells can be provided between the inner shell and the high iodine shell, between the high iodine shell and the intermediate shell, and between the middle shell and the outermost shell, or there is no need to provide one. good. For these arbitrary shells, the above-mentioned method for providing high iodine shells can be similarly used. In the inner shell, high iodine shell, intermediate shell, outermost shell, and arbitrary shells at each position, a desalination step may be carried out according to a conventional method as necessary during the preparation of adjacent shells, or
Shell formation may be performed continuously without performing the desalination step.

Regarding the iodine content of each coating shell of the silver halide grains of the present invention, for example, J, 1. Goldstein (Gol)
dsteln), D.B., William
ms) "X-ray analysis in rTEM/ATEM" Scanning Electron Microscopy (1977
), Volume 1 (IIT Research Institute Vol. 6
It can also be determined by the method described on page 51 (March 1977). J The silver decagenide grains as the final product after the formation of the outermost shell of the present invention are free from excess halogen compounds generated during preparation, by-products or unnecessary salts and compounds such as nitrates and ammonia. It may be removed from the dispersion medium. The removal method can be the Tardel water washing method or dialysis method commonly used for general emulsions, or inorganic salts, anionic surfactants, anionic polymers (e.g. polystyrene sulfonic acid), or gelatin derivatives (e.g. acylated gelatin, carbamoylated gelatin, etc.). ), a flocculation method, etc. can be used as appropriate.

The core/shell type silver halide grains of the present invention can be optically enhanced to a desired wavelength range. There are no particular restrictions on the optical sensitization method, and for example, optical sensitization can be carried out by using cyanine dyes such as zeromethine dyes, monomethine dyes, dimethine dyes, trimethine dyes, or optical enhancers such as merocyanine dyes alone or in combination. be able to. Combinations of sensitizing dyes are often used, especially for the purpose of supersensitization.

Along with sensitizing dyes, dyes that themselves do not have a spectral sensitizing effect or substances that do not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion. These techniques are described in U.S. Patent 2.688.5451.242.
, No. 588, No. 1,293,862, West German patent (OL
S) No. 2.030,326, No. 2,121.780,
Special Publication No. 43-4936, No. 44-14030, Research Disclosure
losure) Volume 176 17643 (December 1978
It is also stated in section 5 of page 23 (issued in March).

The selection can be arbitrarily determined depending on the wavelength range to be degraded, sensitivity, etc., and the purpose and use of the photosensitive material.

The core/shell type silver halide crystals of the present invention can be subjected to various chemical enhancement methods that are applied to general emulsions.

For chemical sensitization, use a bar freezer (H.

Friesew) Die Grundlagen der Fotokrafischen Prosese Mitsut Silberhalogennieden (Die Grundlagen)
der Photo-graPhische Proz
esse 1lIit Silberhalogen
den) (Akademische Verlagsgesellschaft) (Akade+wi pig he Verlagsge
1968) 675
The method described on pages 1 to 734 can be used. That is, a sulfur sensitization method using a compound containing sulfur that can react with silver ions or active gelatin, a reduction sensitization method using a reducing substance, a noble metal sensitization method using gold or other noble metal compounds, etc. are used alone or in combination. be able to. As the sulfur sensitizer, thiosulfates, thioureas, thiazoles, rhodanines, and other compounds can be used, and specific examples thereof are described in U.S. Pat.
No. 10.689, No. 2.278,947, No. 2,728,
No. 668, No. 3,656.955, No. 4.032,928
No. 4,067.740.

As the reduction sensitizer, stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds, etc. can be used, and specific examples thereof can be found in US Pat.
No. 487.850, No. 2.419.974, No. 2.518
．． No. 698, No. 2,983.609, No. 2,983.61
No. 0, No. 2.694.637, No. 3,930.867,
No. 4,054,458. For noble metal sensitization, in addition to gold complex salts, complex salts of metals in Group I of the periodic table, such as platinum, iridium, and palladium, can be used. Specific examples thereof include U.S. Pat.
．． No. 060, UK combination can be used.

The amount of coated silver is arbitrary, but is preferably at least 1,000 ■/d and not more than 15,000 ■/d, more preferably 2
000Qr/m or more and 10000Qr/rrr or less.

Additionally, photosensitive layers containing the particles may be present on both sides of the support. -1 Various dopants can be doped during the formation of each shell of the core/shell type emulsion of the present invention. Examples of this internal dopant include silver, ions, iridium, gold, platinum, osmium, rhodium, tellurium, selenium,
Contains cadmium, zinc, lead, thallium, iron, antimony, dismuth, arsenic, etc.

In order to dope with these dopants, water-soluble salts or complex salts of each type can be present at the time of formation.

As the binder for the core/shell type silver halide grains according to the present invention or the dispersion medium used in their production, hydrophilic colloids commonly used in silver halide emulsions are used. Hydrophilic colloids include not only gelatin (either lime-treated or acid-treated) but also gelatin derivatives, such as gelatin and aromatic sulfonyl chlorides, acid chlorides, as described in U.S. Pat. , gelatin derivatives made by reaction with acid anhydrides, isocyanates, and 1,4-diketones, U.S. Pat.
Gelatin derivatives produced by the reaction of gelatin and trimellitic anhydride as described in Japanese Patent Publication No. 118.766, and gelatin derivatives produced by the reaction of gelatin with an organic acid containing an active halogen as described in Japanese Patent Publication No. 39-5514. , gelatin derivatives produced by the reaction of aromatic glycidyl ether with gelatin, as described in Japanese Patent Publication No. 42-26845, maleimide, maleamic acid, unsaturated aliphatic diamide, etc., and gelatin as described in U.S. Pat. gelatin derivatives by the reaction of British Patent No. 1,033.
189, polyoxyalkylene derivatives of gelatin described in U.S. Pat. esters with hydrohydric or polyhydric alcohols, as well as amides, acrylic (or methacrylic) nitriles, styrene and other vinyl monomers, alone or in combination, grafted onto gelatin; synthetic hydrophilic polymeric substances, such as vinyl alcohol, N-vinylpyrrolidone,
Homopolymers containing monomers such as hydroxyalkyl (meth)acrylate, (meth)acrylamide, N-substituted (meth)acrylamide, etc., or copolymers of these with each other, (meth)acrylic acid esters, vinyl acetate, styrene copolymers of any of the above with maleic anhydride, maleamic acid, etc.; natural hydrophilic polymeric substances other than gelatin, such as casein,
Agar, alkino acid polysaccharides, etc. can also be used alone or in combination.

The silver halide photographic emulsion containing core/shell type silver halide grains according to the present invention can contain various commonly used additives depending on the purpose.

These additives include, for example, azoles or imidazoles, such as benzothiazolium salts, nitroinzoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzthiazoles. , mercaptobenzimidazoles, mercaptothiadiazoles; triazoles, aminotriazoles,
Benzotriazoles, nitrobenzotriazoles;
Tetrazoles, such as mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole);
mercaptopyrimidines; mercaptotriazines, e.g. thioketo compounds such as oxasirithione; azaindenes, e.g. triazaindenes, tetraazaindenes (particularly 4-hydroxy substituted (1,3,3a,
7) Tetraazaindene), pentaazaindene, etc.; Contains stabilizers and antifoggants such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, imidazolium salt, tetrazolium salt, polyhydroxy compound, etc. I can do it.

The photographic light-sensitive material using the core/shell type emulsion of the present invention may contain an infinity or organic hardening agent in the photographic emulsion layer and other hydrophilic colloid layers. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, geltaraldehyde, etc.),
N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2゜3-dihydroxydioxane, etc.), active vinyl compounds (1,3,5-)lyacryloyl-hexahythroS-
triazine, 1,3-vinylsulfonyl-2-propatol, etc.), active halogen compounds (2,4-dichloro-
6-hydroxy-3-triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloric acid, etc.).

These can be used alone or in combination.

Photographic sensitizers using the core/shell type emulsion of the present invention include:
The photographic emulsion layer and other hydrophilic colloid layers may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability.

For example, alkyl (meth)acrylates, alkoxyalkyl (meth)acrylates, glycidyl (meth)acrylates, (meth)acrylamides, vinyl esters (e.g. vinyl acetate), acrylonitrile, olefins, styrene, etc. alone or in combination, or these and acrylic acid, A polymer containing a combination of methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl(meth)acrylate, sulfoalkyl(meth)acrylate, styrene sulfonic acid, etc. as a monomer component can be used. 1. The silver halide photographic light-sensitive material according to the present invention may optionally contain a development accelerator such as benzyl alcohol or a polyoxyethylene compound; an image stabilizer such as Chroman, Claman, bisphenol, or phosphite ester. ;wax,
It may contain lubricants such as glycerides of higher fatty acids and higher alcohol esters of higher fatty acids, development regulators, developing agents, plasticizers, and bleaching agents. Surfactants that may be included include anionic, cationic, and nonionic coating aids, permeability improvers for processing solutions, antifoaming agents, and materials for controlling various physical properties of photosensitive materials. A variety of types or bisexual types can be used. As the antistatic agent, diacetyl cellulose, styrene perfluoroalkyl sodium maleate copolymer, alkali salt of a reaction product of styrene-maleic anhydride copolymer and p-aminobenzenesulfonic acid, etc. are effective. Examples of matting agents include polymethyl methacrylate, polystyrene, and alkali-soluble polymers. It is also possible to use colloidal silicon oxide. Further, examples of the latex added to improve the physical properties of the film include copolymers of acrylic esters, vinyl esters, etc., and other monomers having ethylene groups. Examples of gelatin plasticizers include glycerin and glycol compounds, and examples of thickeners include styrene-maleic acid sorta copolymer, alkyl vinyl ether-maleic acid copolymer, and the like.

The emulsion containing silver halide grains of the present invention can have rich latitude by mixing at least two emulsions having different average grain sizes but different sensitivities, or by coating in multiple layers.

The mixed silver salt crystal according to the present invention is black and white general use, X.

Effective for photosensitive materials for various uses such as ray, color, infrared, micro, silver dye bleaching, reversal, diffusion transfer, high contrast, photothermography, and heat-developable materials. However, it is particularly suitable for highly sensitive color photosensitive materials.

In order to apply the core/shell type silver halide emulsion according to the present invention to a color photographic light-sensitive material, an emulsion containing the above-mentioned crystals of the present invention adjusted to have red sensitivity, green sensitivity and blue sensitivity is added to cyan, magenta and Techniques and materials used for color photosensitive materials may be used, such as incorporating a combination of yellow couplers. For example, magenta couplers include 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazolotriazole couplers, cyanoacetylcoumaron couplers, open-chain acylacetonitrile couplers, and yellow couplers include acylacetamide couplers (e.g., benzoylacetanilides, Examples of cyan couplers include naphthol couplers and phenol couplers. These couplers are preferably non-diffusive and have a hydrophobic group called a ballast group in the molecule. The coupler may be either 4-equivalent or 2-equivalent to silver ion. It may also be a colored coupler that has a color correction effect or a coupler that releases a development inhibitor during development (so-called DIR coupler). In addition to DIR couplers, there are also colorless DIR couplers in which the product of the coupling reaction is colorless and releases a development inhibitor.
May include campling.

In carrying out the present invention, the following known anti-fading agents may be used in combination, and the color image stabilizers used in the present invention may be used alone or in combination of two or more. Known antifading agents include hydroquinone derivatives, gallic acid derivatives, p-alkoxyphenols, p-oxyphenol derivatives, and bisphenols.

The photosensitive material of the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, benzotriazole compounds, 4-thiazolidone compounds, benzophenone compounds, cinnamic acid ester compounds, butadiene compounds, benzoxazole compounds, and ultraviolet-absorbing polymers substituted with an aryol group can be used. These ultraviolet absorbers may be fixed in the hydrophilic colloid layer.

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

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

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

The invention is also applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support.

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

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other hydrophilic colloid layers can be coated on the support or other layers by various known coating methods, including tip coating, roller coating, and curtain coating. A coating method, an extrusion coating method, etc. can be used. The methods described in U.S. Pat. Nos. 2,681.294, 2,761.791 and 3.526.528 are advantageous.

Supports for photographic materials include, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass, cellulose acetate, cellulose nitrate, polyvinyl acecool, volimistry (Photogra
phic Processing Chemistry
) Published by Focal Press,
1966), pp. 226-229, U.S. Patent No. 2.193.
．． No. 015, No. 2,592.364, Japanese Unexamined Patent Publication No. 1973-6
Those described in No. 4933 and the like may be used.

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

After color development, the photographic emulsion layer is usually bleached. Bleaching treatment may be carried out simultaneously with fixing treatment, or may be carried out separately. Bleaching agents include iron (■) and cobalt (■).
), chromium (■), compounds of polyvalent metals such as copper (II), peracids, quinones, nitroso compounds, etc. are used.

For bleaching or bleach-fixing solutions, U.S. Patent 3,042.52
No. 0, No. 3,241.966, Special Publication No. 45-8506
Various processing methods can be applied, but representative ones include a method in which a bleach-fixing process is performed after color development, followed by water washing and stabilization treatment if necessary, or a method in which bleaching and fixing are performed after color development. It is possible to apply a method of separating and performing further washing and stabilization treatment as necessary. The color developing solution is generally an alkaline aqueous solution containing a color developing agent.The color developing agent is a known primary aromatic amine developer, such as phenylene diamines (e.g. 4-amino-N, N-diethylaniline, 3-
Methyl-4-amino-N,N-diethylaniline, 4-
Amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N
-ethyl-N-β-methanesulfamide ethylaniline, 4-amino-3-methyl-N-ethyl-N-β-methoxyethylaniline, etc.) can be used.

In addition, L.F.A.Mason (L, F, A.

Photographic Processing by Kepropylene, for example, polyester films such as polyethylene terephthalate, polystyrene, and other commonly used materials can be appropriately selected depending on the purpose of use of each photographic light-sensitive material.

These supports are subjected to undercoat processing if necessary.

After exposure, the photographic sensitizer containing the core/chef type silver halide emulsion according to the present invention can be developed by a commonly used known method.

The black and white developer is an alkaline solution containing developing agents such as hydroxybenzenes, aminophenols, and aminobenzenes, and other alkali metal salts such as sulfites, carbonates,
May include bisulfites, bromides, iodides, and the like. Further, when the photographic light-sensitive material is for color use, color development can be carried out by a commonly used color development method. In the reversal process, the image is first developed with a black-and-white negative developer, then exposed to white light or treated with a bath containing a capri agent, and then color developed with an alkaline developer containing a color developing agent. There are no particular restrictions on the treatment method, and in addition to the bleaching accelerator described in JP-A No. 15-8836 and the thiol compound described in JP-A-53-55732, various additives can also be added.

Next, an example of producing silver halide grains according to the present invention will be specifically explained.

11 Synthesis (1-1) Production of inner core: A silver iodobromide emulsion EM-1 containing 4 mol % of silver iodide was prepared using the six types of solutions shown below.

(Solution A-1) Ossein gelatin 39.7 g Distilled water 3936 mj! Polyisopropylene-polyethyleneoxydisuccinate ester (thorium salt 10% ethanol solution 35.4ml Magnesium sulfate 3.6g 6% nitric acid 75.6mj! Potassium bromide 2.06 g (Solution B-
1) Ossein gelatin 35.4 g Potassium bromide 807 g Potassium iodide 47 g Polyisopropylene-polyethyleneoxydisuccinate ester sodium salt 10% ethanol aqueous solution 35.4 mj!
Distilled water 1432mf (solution E-1) Silver nitrate 240g 6% nitric acid 52ml Distilled water
1467mj! (Solution F-1) 25% KBr aqueous solution Required amount for pAg adjustment (Solution H-1) 6% Nitric acid Required amount for pH adjustment (Solution 1)
-1) 7% sodium carbonate aqueous solution pH adjustment required amount at 40°C, JP-A-57-92523, JP-A-57-9252
Add solution E to solution A-1 using the mixer shown in No. 4.
-1 and B-1 were added by simultaneous mixing method. The pAg, pH, and addition rate of solutions E-1 and B-1 during simultaneous mixing were controlled as shown in Table 1.

The pAg and pH were controlled by changing the flow rates of solution F-1 and solution H-1 using a variable flow rate roller tube pump.

3 minutes after the addition of solution E-1 is completed, the pH is adjusted with solution I-1.
was adjusted to 5.5.

Next, the mixture was washed with demineralized water in a conventional manner and dispersed in an aqueous solution containing 125 g of ossein gelatin, and the total volume was adjusted to 4800 ml with distilled water.

According to electron microscopy, this emulsion has an average grain size of 0.09.
It was found that the emulsion was a monodisperse emulsion of μm. Note that the particle size here refers to the side length when the volume of the particle is converted into a cube having the same volume, and the same applies to the following description.

(Leaving space below) Table 1 (1-2) Addition of fifth shell: Using the five types of solutions shown below, use the above EM-1 as a seed emulsion, and add iodine with a silver iodide content of 2 mol%. Emulsion EM-2 provided with a silver bromide shell was prepared.

(Solution A-2) Ossein gelatin 34.54 g Distilled water 8642 ml Polyisobrobylene-polyethyleneoxydisuccinate ester sodium salt 10% ethanol solution 20 ml 14-
Hydroxy-6-methyl-1,3,3a,7-thitraazaindene 181.32 mg
28% ammonia water 117.4 m
156% acetic acid aqueous solution 154 ml
! Magnesium sulfate 16 g Seed emulsion (EM-1) 0.329 mol equivalent (solution B-2) Ossein gelatin 18.72 gK
Br763.
8 gKl
21.8g 4-Hydroxy-6-methyl-1,3,3a,7-thitraazaindene 2.17g Magnesium sulfate 7.4g Distilled water
1578 ml (Solution E-
2) A g NO31142.4g 28% ammonia water 931.4m
Make up to 1921ml with Il distilled water.

(Solution F-2) 50% KBr aqueous solution Required amount for pAg adjustment (Solution G-2) 56% acetic acid aqueous solution Required amount for pH adjustment 40°C
In JP-A No. 57-92523, No. 57-9252
Using the mixer shown in No. 4, add solution E to solution A-2.
-2 and solution B-2 were added by a simultaneous mixing method over a minimum time of 32.5 minutes without generation of small particles. The addition rates of 1) Ag, p) I and solutions E-2 and B-2 during simultaneous mixing were continuously controlled as shown in Table 2. pAg
The pH was controlled by changing the flow rates of solution F-2, solution G-2, and solution B-2 using a roller tube pump with variable flow rate.

After the addition of solution E-2 was completed, pAg was adjusted to 10.4 with solution G-2, and 2 minutes later, pAg was adjusted to 6.0 with solution F-2.

Table 2 Next, the mixture was washed with demineralized water using a conventional method and dispersed in an aqueous solution containing 128.6 g of ossein gelatin, and the total volume was adjusted to 3000 ml with distilled water.

According to electron microscopy, this emulsion has an average grain size of 0.27.
It was found that the emulsion was a highly monodisperse emulsion with a variation coefficient of μm particle size distribution of 12%.

(1-3) Adding a fourth shell: Using the five types of solutions shown below, use the above EM-2 as a seed emulsion, and add a shell of silver iodobromide with a silver iodide content of 2.6 mol%. Emulsion EM-3 was prepared.

(Solution A-3) Ossein gelatin 34.0 g Distilled water 7779 mj! Polyisopropylene-polyethyleneoxydisuccinate ester sodium salt 10% ethanol solution 20m #4-hydroxy-6-methyl-1,3,3a,? -Tetraazaindene 405 mg28
%Ammonia water 117.3m 15
6% acetic acid aqueous solution 12ml type 1 emulsion (
EM-2) 0.303 mol equivalent (solution B
-3) Ossein gelatin 18.74 gK
Br 760.2 gK
l 28.4g4-hydroxy-6-methyl-1,3,3a,? -Tetraazaindene 1.35 g Distilled water 1574 ml (
Solution E-3) A g N 03 1.148
g28% ammonia water 937m
1 Make up to 1930ml with distilled water.

(Solution F-3) 50% KBr aqueous solution pA & required amount for adjustment (Solution G-3) 56% acetic acid aqueous solution Required amount for pH adjustment 40°C
In JP-A No. 57-92523, No. 57-9252
Using the mixer shown in No. 4, add solution E to solution A-3.
-3 and solution B-3 were added by a simultaneous mixing method over a minimum time of 56.5 minutes during which no small particles were generated. The addition rates of pAg, p)1 and solutions E-3 and B-3 during simultaneous mixing were controlled as shown in Table 3. pAg and pH are controlled by a roller tube pump with variable flow rate.
-3, while changing the flow rates of solution G-3 and solution B-3.

Two minutes after the addition of solution E-3 was completed, the pA was adjusted by solution G-3.
g to 10.4 and after another 2 minutes pH with solution F-3.
was adjusted to 6.0.

Next, the mixture was washed with demineralized water in a conventional manner and dispersed in an aqueous solution containing 128.1 g of ossein gelatin, and the total amount was adjusted to 3000 ml with distilled water.

According to electron microscopy, this emulsion has an average grain size of 0.80.
It was found that the emulsion was a highly monodisperse emulsion with a coefficient of variation in μm and particle size distribution of 10%.

(Leaving space below) Table 3 (1-4) Application of high iodine shell, intermediate shell, and outermost shell of the present invention: Using the seven types of solutions shown below, the above EM-3 was used as a seed emulsion, and the present invention An emulsion EM-4 was prepared which was provided with a high iodine shell, an intermediate shell, and an outermost shell according to the invention.

(Solution A-4) Ossein gelatin 22.5 g Distilled water 6884 ml Polyisopropylene-polyethyleneoxydisuccinate ester sodium salt 10% ethanol solution 20 mβ4
-Hydroxy-6-methyl-1,L3a,? -Tetraazaindene 28% ammonia water in the amount listed in Table 4 469 mj! 56% acetic acid aqueous solution 258mf seed emulsion
0.8828 mol equivalent amount (solution B-4) Ossein gelatin 24 gKBr
Quantity KI listed in Table-5
Amount of 4-hydroxy-6 listed in Table-5
-Methyl- 1,3,3a,? -Tetraazaindene Distilled water in the amount listed in Table-5
1978 mj! (Solution C
-4) Ossein gelatin 24 gKBr
Quantity Kl listed in Table-6
Amount of 4-hydroxy-6 listed in Table-6
-Methyl- 1,3,3a,7-thitraazaindene Distilled water in the amount listed in Table 6
1978 ml (Solution D-
4) Ossein gelatin 40 gKBr
Quantity Kl listed in Table-7
Amount of 4-hydroxy-6 listed in Table-7
-Methyl- 1,3,3a,? -Tetraazaindene Distilled water in the amount listed in Table-7
3296 ml (solution E-
4) AgNO+ 1109 g
28% ammonia water 904ml Make up to 1866ml with distilled water.

(Solution F-4) 50% KBr aqueous solution 1) Required amount for Ag adjustment (Solution G-4) 56% acetic acid aqueous solution Required amount for pH adjustment 50°C
In JP-A No. 57-92523, No. 57-9252
Add solution E to solution A-4 using the mixer shown in No. 4.
-4 and solution B-4 were added for 46.6 minutes by the simultaneous mixing method, and C-4 was added at the same time as the addition of B-4 was completed.
．． At the same time as the addition of C-4 was completed after 9 minutes, D-4 was added, and the addition was completed after 25.5 minutes. pA during simultaneous mixing
gSpH and the addition rate of solutions E-4, B-4, C-4, and D-4 were controlled as shown in Table-8. pAg and pn
This was controlled by changing the flow rates of solution F-4 and solution G-4 using a variable flow rate roller tube pump.

Two minutes after the addition of solution E-4 was completed, the pA was adjusted with solution F-4.
g to 10.4 and after another 2 minutes pH with solution G-4.
was adjusted to 6.0.

Next, after washing with demineralized water using a conventional method and dispersing it in an aqueous solution containing 127 g of ossein gelatin, a total amount of 3
The volume was adjusted to 000 ml.

According to electron microscopy, this emulsion has an average grain size of 1.60.
It was found to be a highly monodisperse emulsion with a coefficient of variation in μm and particle size distribution of 11%.

EM-4 is a core/shell type silver iodobromide emulsion with silver iodide contents of 15 mol %, 5 mol % and 0.3 mol % sequentially from the grain interior (i.e. Iz = 0.3, Th =
0.5 , ■, , = 5 is Xun.

(Leaving space below) Table-4 Table-5 Table-6 Solution C-4 Preparation Amount Table-7 Solution D-4 Preparation Amount Table-8 Using the seven types of solutions shown in (1-4) of Production Example 1, K
BrSKI and 4-hydroxy-6-methyl-1,3,
3a,? - Table 4, 5, 6 for the amount of tetraazaindene added.
EM-5, EM-6, EM-7, EM-8, EM-5, EM-6, EM-7, EM-8,
EM-9 was manufactured.

These are monodispersed emulsions with an average grain size of 1.60 μm, and the coefficients of variation in grain size distribution are 17%, 15%, 12%, respectively.
They were 16% and 16%.

Using the seven types of solutions shown in (1-4) of Ibaku Production Example 1, K
Br, KI and 4-hydroxy-6-methyl-1,3,
Table 4, 5, 6 shows the adjusted amount of 3a, 7-chitraazaindene.
EM-10 to EM-26 were produced in the same manner as in Production Example 1 (1-4) except that the amounts described in , 7 were used.

These are monodisperse emulsions with an average grain size of 1.60 μm, and the coefficients of variation in grain size distribution are 10%, 10%, 11%, and 11%, respectively.
12%, 13%, 18%, 19%, 35%, 39%, 1
0%, 11%, 11%, 11%, 12%, 12%, 12
%, 13%.

Using the seven types of solutions shown in (1-4) of Production Example 1, K
Br, KI and 4-hydroxy-6-methyl-1,3,
Table 4, 5, 6 shows the adjusted amount of 3a, 7-chitraazaindene.
EM-28 and EM-29 were produced in the same manner as in Production Example 1 (1-4) using the amounts described in , 7.

Furthermore, pAg, pH and E-4, B-4, C during mixing
-4, the addition rate of D-4 was controlled as shown in Table-9.
EM-27 was manufactured by changing the method, and EM-30 and EM-31 were manufactured as shown in Table 10.

These are monodispersed emulsions with an average grain size of 1.6 μm, and the coefficients of variation in grain size distribution are 9%, 18%, 19%, and 3, respectively.
2% and 34%.

Table-9 Back-10 Using the seven types of solutions shown in (1-4) of Production Example 1, K
Br, KI and 4-hydroxy-6-methyl-1,3,
3a,? - Table 4, 5, 6 for the adjusted amount of tetraazaindene.
, 7, and further, p, Ag, pH during mixing.
The control of the addition rate of E-4, B-4, C-4, and D-4 was changed as shown in Table 11, and EM-32 was added to EM-32 as shown in Table 12. EM-34 was manufactured as shown in Table 13.

These were monodisperse emulsions with an average grain size of 1.6 μm, and the coefficients of variation in grain size distribution were 10%, 10%, and 12%, respectively.

Table-11 Table-12 Table-13 Using the seven types of solutions shown in (1-4) of 1fl Main Production Example 1, K
Br, KI and 4-hydroxy-6-methyJLt-1,
Table 4, 5 shows the amount of 3,3a,7-chitraazaindene adjusted.
, 6, and 7, except for the amounts described in (1-4) of Production Example 1.
EM-35, 36, and 37 were produced in the same manner as above.

Furthermore, pAg during mixing, pH and E-4, B-4,
EM-38 and EM-39 were produced by changing the control of the addition rate of C-4 and D-4 as shown in Table 12.

These are monodisperse emulsions with an average grain size of 1.6 μm, and the coefficients of variation in grain size distribution are 12%, 14%, 13%, and 13%, respectively.
They were 9% and 11%.

E, Example Next, the present invention will be described in more detail with reference to examples.

<Example 1> EM-5, EM-6, EM-7, EM-4, E described above
The effect of the intermediate shell will be shown using M-8 and EM-9.

Effects on sensitivity, fog, granularity, exposure range width, sharpness, and multilayer sensitivity were investigated.

A single layer sample was prepared and measured for sensitivity, capri, granularity, exposure range width, and sharpness.

For multilayer sensitivity, a multilayer color photosensitive material having three color photosensitive layers of blue sensitivity, green sensitivity, and red sensitivity was prepared and the effect was investigated.

Next, we will describe how to prepare each sample and how to measure each performance.

Preparation of a single color-sensitive coated sample (single layer): Here, a case will be described in which the present invention is applied to a sample consisting of a two-layer photosensitive material, one emulsion layer containing a coupler and a protective layer.

In this example, a magenta coloring coupler was used.

Specifically, in this example, 1-(2,4,6-dolichlorophenyl)-3 was used as the magenta coloring coupler.
-(3-(2,4-di-t-amylphenoxyacetamide)benzamide to 5-pyrazolone was used.

Tricresyl phosphate (TCP) was used as a high boiling point solvent to dissolve the coupler.

The coupler was oil-protected and dispersed according to a conventional method.

Silver iodobromide emulsions (EM-4 to EM-9) shown in the above production examples
) was subjected to chemical sensitization according to a conventional method, and further color sensitized to green sensitivity using a green sensitizing dye during chemical sensitization according to a conventional method.

(1.8 g of this chemically sensitized and color sensitized silver iodobromide emulsion
).

Each layer in this example was adjusted as follows.

1st layer: Highly sensitive green-sensitive emulsion containing 1.9 g of gelatin and 0.06 g of DNP (ditertiary-nonylphenol) dispersion in which 0.20 g of magenta coupler and 0.049 g of color magenta coupler are dissolved. layer.

Second layer...Yellow containing 0.15g yellow colloidal silver, 0.118 DBP (dibutyl terephthalate dispersion) with 0.2g antifouling agent dissolved and 1.5g gelatin.
One layer of filters.

In addition to the above composition, a gelatin hardener and a surfactant were added to each of the two layers.

Each sample was subjected to conventional wedge exposure for measurements of sensitometric performance (sensitivity, exposure range, fog) and graininess, and square wave frequency wedge exposure for sharpness measurements, followed by subsequent processing. processed in the process.

Processing steps: Color development 3 minutes 15 seconds bleaching 6 minutes 30 seconds water
Wash 3 minutes 15 seconds Fix
Wash with water for 6 minutes and 30 seconds
Stabilization for 3 minutes and 15 seconds Drying for 1 minute and 30 seconds The composition of the treatment liquid used in each treatment step is shown below.

[Color developer]

4-Amine-3-methyl-N-(β-hydroxyethyl)-aniline sulfate 4.57 g Anhydrous sodium sulfite 4.25 g Hydroxylamine sulfate 2.0 g Anhydrous potassium carbonate
37.5 g sodium bromide
Add 1.3g nitrilotriacetic acid trisodium salt (monohydrate) 2.5g potassium hydroxide 1.0g water to make 11.

[Bleach solution]

Ethylenediaminetetraacetic acid iron ammonium salt 100.
0 g Ethylenediaminetetraacetic acid diammonium salt 10.0
g Ammotium bromide 150.0 g
Add 10.0 ml of glacial acetic acid to make IIl, and adjust to pH 6.0 using aqueous ammonia.
Adjust to.

[Fixer]

Ammonium thiosulfate 175.0 g
Anhydrous ammonium sulfite 8.68 Sodium metasulfite 2.3g Add water to 11
and adjusted to p) 16.0 using acetic acid.

[Stabilizing liquid]

Formalin (37% aqueous solution) t, sm
1 Konidax (manufactured by Konishiroku Photo Industry Co., Ltd.) 7.5m
l Add water to make 11.

The developed samples were subjected to sensitometric measurements, granularity measurements, and sharpness measurements using green light.

Fog: The lowest optical density of the so-called characteristic curve obtained by sensitometry (the larger the value, the higher the fog, which is undesirable).

Sensitivity: Reciprocal of the exposure amount (anti-value) that gives an optical density of fog + 0.1 on the characteristic curve (In the table of results of examples, the sensitivity of the comparative emulsion is expressed as 100 and expressed as a relative value: the larger the value (The faster the sensitivity, the better.)

Sharpness: Detection of the improvement effect of image sharpness is performed using MTF (
Modulation Transfer Function
ion) and compared the MTF size of 10 spatial frequencies/tsuru. The larger the value, the better.

Graininess...RMS: Dye image density is Do+in+
The value of 1000 times the standard deviation of the variation in density value that occurs when a 0.8 dye image is scanned by a microdensitometer with a circular scanning aperture of 25 μm is expressed as a relative value with the control sample as 100. The larger the value, the coarser the grains, which is not preferable.

Width of exposure range: Exposure amount (logarithmic value) that gives an optical density of turn lJ+0.1 on the characteristic curve and maximum optical density -0,
The larger the difference between the exposure doses (logarithmic value) giving an optical density of 1, the wider the exposure range, which is preferable.

Preparation of multilayer color photosensitive material (referred to as multilayer sample): Silver iodobromide emulsions (EM-4 to EM-9) shown in the above production example
) was subjected to chemical sensitization according to a conventional method, and a color photosensitive material consisting of nine layers having three types of photosensitive layers: a blue photosensitive layer, a green photosensitive layer, and a red photosensitive layer was prepared in the following manner. In the chemically sensitized emulsions EM-4 to EM-9, only the green-sensitive high-speed layer (fifth layer) was changed. The other photosensitive layer is
A completely common emulsion was used in each sample.

It consists of a subbed cellulose triacetate film with an antihalation layer (0.40 g of black colloidal silver).
and 3.0 g of gelatin. ) A sample was prepared by coating each of the following layers in order on a transparent support. In all of the following examples, the amount added to the light-sensitive material is shown per 1 d, and the amounts of silver halide emulsion and colloidal silver are shown in terms of silver.

Layer 1: 1.4 g of low-sensitivity red-sensitive silver iodobromide (containing 7 mol% silver iodide) emulsion layer color-sensitized to red sensitivity and 1.2 g of red-sensitized silver iodobromide emulsion layer.
of gelatin and 0.8 g of 1-hydroxy-4-(β
-methoxyethylaminocarbonylmethoxy)-N-(
δ-(2,4-di-t-amylphenoxy)butyl-2-naphthamide [hereinafter referred to as C-1]. ], 0.07
5 g of 1-hydroxy-4-(4-(1-hydroxy-
δ-acetamido-3,6-disulfo-2-naphthylazo)phenoxy)-N-(δ-(2,4-di-t-amylphenoxy)butyl-2-naphthamide disodium [hereinafter referred to as colored cyan coupler (CC) -1)] and 0.015 g of 1-hydroxy-2[δ-(
2,4-di-t-amylphenoxy)n-butyl]naphthamide, 0.07 g of 4-octadecylsuccinimide-2-(1-phenyl-5-tetrazolylthio)-1
-Indanone [hereinafter referred to as DIR compound (D-1).

] in 0.65 g of tricresyl phosphate-4 (
A low-sensitivity red-sensitive emulsion layer (hereinafter referred to as RL) containing TCP)
layers).

Ji2...1.3 g of high-sensitivity red-sensitive silver iodobromide emulsion 1.
2g gelatin and 0.21g cyan coupler (C-
1) and 0.02 g of colored cyan coupler (CC-
A highly sensitive red-sensitive emulsion layer (hereinafter referred to as RH layer) containing 0.23 g of TCP in which 1) was dissolved.

Layer 3: 0.07 g of 2.5-di-t-octylhydroquinone [hereinafter referred to as antifouling agent (HQ-1).

] was dissolved in 0.04 g of n-dibutyl phthalate [hereinafter referred to as DBP]. ] and an intermediate layer (hereinafter referred to as IL) containing 0.8 g of gelatin.

Layer 4: 0, 80 g of low-sensitivity silver iodobromide (containing 6 mol% silver iodide) emulsion sensitized to green sensitivity, 2.2 g of gelatin, and 0.8 g of 1-<2.4 .6-trichlorophenyl)3-(3-(2゜4-di-t-amylphenoxyacetamide)benzamide-5-pyrazolone (hereinafter referred to as magenta coupler (M-1)), 0.15
g of 1-(2,4,6-1-lichlorophenyl')-4
-(1-naphthylazo)-3-(2-chloro-5-octadecenylsuccinimideanilino)-5-pyrazolone [hereinafter referred to as colored magenta coupler (CM-1). ), a low-speed green-sensitive emulsion layer (hereinafter referred to as OL) containing 0.95 g of TCP in which 0.016 g of DIR compound (D-1) was dissolved.

Layer 5: 1.8 g of high-sensitivity green-sensitive silver iodobromide emulsion color sensitized to green sensitivity, 1.9 g of gelatin and 0.20 g
of magenta coupler (M-1), and 0.2 in which 0.049 g of colored magenta coupler (CM-1) was dissolved.
High-sensitivity green-sensitive emulsion layer (hereinafter referred to as GH) containing 5g of TCP
).

Layer 6: One layer of yellow filter (hereinafter referred to as yc) containing 0.15 g of yellow colloidal silver, 0.11 g of DBP in which 0.2 g of antifouling agent (HQ-1) was dissolved, and 1.5 g of gelatin. ).

Layer 7: 0.2 g of low-speed bromide SR (containing 4 mol% silver iodide) emulsion sensitized to blue sensitivity, 1.9 g of gelatin, and 1.5 g of α-pivaloyl-α- (1-Benzyl-2-phenyl-3,5-thioxoimidazolidin-4-yl)-2'-chloro-5'-[α-dodecyloxycarbonyl)ethoxycarbonyl]acedoanilide [hereinafter referred to as Y-1] . ] 0.6g of T dissolved in
Low-speed blue-sensitive emulsion layer containing CP (hereinafter referred to as BL)
.

Layer 8: 1.0 g of high-sensitivity silver iodobromide emulsion sensitized to blue sensitivity, 1.5 g of gelatin, and 0.65 g of TCP in which 1.30 g of yellow coupler (Y-1) was dissolved.
A high-speed blue-sensitive emulsion layer (hereinafter referred to as BH) containing.

Layer 9...protective layer (hereinafter referred to as P) containing 2.3 g of gelatin
R).

Measurement of multilayer sensitivity: The thus prepared multilayer color photosensitive material was exposed to white wedge light according to a conventional method, processed in the above processing steps, and green light sensitivity was obtained by sensitometric measurement (the definition of sensitivity is Same as for the single color-sensitive coated sample).

Results of Example 1 (Effect of intermediate shell): Table 15 shows the results of fog, sensitivity, granularity, width of exposure range, sharpness of the single color-sensitive coated sample, and sensitivity of the multilayer sample.

Conventional core/shell emulsions without an intermediate shell with intermediate iodine content between the outermost shell (low iodine shell) and high iodine shell (
EM-5, EM-9) and core/shell emulsions that have an intermediate shell but have a sufficiently similar iodine content between the high iodine shell and the intermediate shell (
EM-6) and a core/shell emulsion (EM-8) in which there is no sufficient difference in iodine content between the outermost shell and the middle shell. Core/shell emulsions with shells (EM-4, EM-7) provide very high sensitivity.

In addition, this effect is more remarkable in multilayer sensitivity, and the core/shell emulsion of the present invention can be used in multilayer color light-sensitive materials.
It turns out to be more effective.

Further, core/shell emulsions other than those of the present invention tend to have a wide particle size distribution and tend to have high fog, and are also unfavorable in this respect.

<Example 2) The above production examples OEM-4, EM-5, EM-9 to EM-1
Table 16 shows the effect of the iodine content of the high iodine shell using the same method as in Example 1.

EM-10 to EM-15 are examples in which the middle shell and the outermost shell are the same, and the iodine content of the high iodine shell is changed, but as the iodine content of the high iodine shell increases, the iodine content increases. I understand that it becomes sensitive.

Emulsions with high iodine shells having an iodine content of 40 mol% or 50 mol% (EM-15, BM-17) tend to have a small sensitizing effect, but this is due to a wide grain size distribution. This is thought to be due to the fact that emulsions other than the present invention having the same high iodine shell (
It can be seen that the emulsion of the present invention provides a sufficient sensitizing effect when compared with EM-16 and EM-18).

<Example 3> Similarly, the effect of the iodine content of the low iodine shell and the intermediate shell is shown in Table-1.
7.

The lower the iodine content of the outermost shell, the greater the aggravating effect of the present invention.

Especially in multilayer sensitivity, the lower the iodine content in the outermost shell, the greater the effect. Emulsions with high iodine content in low iodine shells (more than 10 mol %...EM-26) have lower sensitivity than comparative emulsions.

<Example 4> Similarly, Table 18 shows the effect of particle size distribution.

The sensitizing effect of the present invention can be more effectively obtained in a monodisperse emulsion with a narrow particle size distribution.

Emulsions with a wide distribution are inferior to emulsions with a narrower distribution in terms of fog and sharpness. As an emulsion with excellent sensitivity and fog sharpness, the monodisperse emulsion of the present invention is more preferable.

<Example 5> Similarly, Table 19 shows the effect of the volume of high iodine shells.

The sensitizing effect of the present invention is due to the volume of high iodine shell being 5% (E M
-33), which worsens the condition in small doses, but the effect is small;
2% (EM-32), 22% (EM-33), 41%
More favorable effects can be obtained in the emulsion (EM-34) having a relatively large volume of high iodine shells.

<Example 6> Similarly, Table 19 shows the effect of the total iodine content of the entire silver iodobromide.

In the present invention, emulsions with a relatively high total iodine content have a small sensitizing effect (EM-35, EM-36), and emulsions with a low total iodine content (EM-38) have poor graininess, sharpness, In order to obtain high sensitivity, excellent graininess, sharpness, and a wide exposure range, it is preferable to use the emulsion of the present invention having an iodine content within an appropriate range. Recognize.

(Leaving space below) (Voluntary) Proceedings J. 31, 1985 Mr. Manabu Shiga, Commissioner of the Patent Office 1. Indication of the case 1985 Patent Application No. 86659 2. Name of the invention Silver halide photographic sensitization Material 3: Relationship with the case of the person making the amendment Patent applicant address: 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name:
(127) Roku Konishi Photo Industry Co., Ltd. Representative Keio Ide 4, Agent 6, Number of inventions to be increased by amendment (1), “Measure” on page 5, line 3 of the specification is corrected to “plan” .

(2), "High iodine content shell" in lines 17 and 20 of page 7 is corrected to "high iodine shell".

(3), "Silver iodobromide" on page 8, line 7 is corrected to "silver iodide."

(4), ``kara'' in line 14 on page 13 is corrected to ``shell''.

(5), r(-)J on page 14, lines 16 and 18
Correct each as "(arbitrary shell)".

(6), "Optional insertion shell" in lines 13 and 15 of page 15 is corrected to "arbitrary shell."

(7), page 188, line 7 r Photohraph
Correct iqueJ to r PhotographiqueJ.

(8), page 188, line 9, "Danfin" is corrected to "Danin".

(9), rchimistry on page 18, line 11
Correct J to rchemistry J.

(10), page 199, line 3, ``to be formed'' is corrected to ``to be formed''.

(11) ``Control'' on page 19, line 13, page 22, line 10, and line 177, page 23, line 7 will be corrected to ``condroldo.''

(12) On page 20, lines 2 and 3, ``but may also'' be corrected to ``may be, also.''

(13) In the 4th line of page 20, change “Kataru” to “
"You can do that," he corrected.

(14) In the second line from the bottom of page 20, "this formed" is corrected to "this high-iodity shell formed."

(15), "Potassium" on page 21, line 6 of the same page is replaced with "
(potassium)".

(16), on page 22, line 6, ``the foregoing'' is replaced with ``
I am correcting it as "the one of the internal core mentioned above."

(17), page 23, lines 5, 122, and 166, "inner shell" is corrected to "inner core."

(1B), ``High iodine shell'' on page 23, line 5 is corrected to ``High iodine shell and intermediate shell.''

(19), page 24, line 4, rGoldsteln
Correct J to rGoldstein J.

(20) On page 24, line 7, "Institute" is corrected to "Institute."

(21), same No. 24, lines 13-14, "Compounds......may be" is corrected to "Compounds may be removed from the dispersion medium of the particles." To do.

(22), "Coagulation precipitation" which is missing on page 24 of the same page is corrected to "Coagulation precipitation".

(23), ``Sore'' on page 25, line 10.
I will correct it.

(24), p. 26, line 8 rFriesew J
Correct it to rFrieser J.

(25), p. 26, lO-11th line rPhoto
graphische J rPhotography
I will correct it as schenJ.

(26) ``Chemical sensitization method'' on page 27, line 16 is corrected to ``chemical sensitization method''.

(27), on page 28, lines 5 and 6, "ion" is corrected to "sulfur."

(2B) ``Jismuth'' in line 8 on page 28 is corrected to ``bismuth.''

(29), "Nitrile" in the third line from the bottom of page 29 is corrected to "Nitrile".

(30), on page 30, line 10, “alkynoic acid” is replaced with “
I corrected it to "alginate".

(31) On page 30, line 4 from the bottom, "Nitroinzoles" is corrected to "Nitroindazoles."

(32), “Oxasilithion” on page 31, line 7
Correct "oxazolinthion" °C.

(33) In the second line from the bottom of No. 31, "infinite" is corrected to "inorganic".

(34) Delete "." on page 32, line 11.

(35), on page 32, lines 15-16, "insoluble or sparingly soluble in water" is corrected to "insoluble or sparingly soluble in water."

(36), "Alki" in the 4th line of page 33 is corrected to "alkyl".

(37) On page 34, line 4 from the bottom, "Different" is corrected to "Different."

(38), “hybrid silver salt crystal” on page 35, line 1 of the same page is replaced with “
Corrected to ``core/shell type silver halide emulsion''.

(39), ``so-called'' in line 8 on page 36 is corrected to ``no coloration''.

(40), p. 36, lines 11-12, ``coupling'' is corrected to ``force...l-pulling compound.''

(41) ``Also used in the present invention'' on page 36, line 14 of the same is deleted.

(42), on page 38, line 12, “can be applied” is replaced with “
Can be applied. ” I am corrected.

(43) On page 39, line 8, "Photographic photosensitive agent" is corrected to "Photographic photosensitive material."

(44), p. 41, lines 1-2, rchemist
ry) focal” to “chen+1stry)”
* Corrected as (focal).

(45) On page 41, line 6, "buffer" is corrected to "buffer,"

(46), on page 41, line 15, ``demayoi'' is corrected to ``demayoi,''.

(47), page 70, lines 9-10, “(This...
・・・・・・1.8 g) , Delete J.

(4B), p. 70, line 13, rl, 9gJ is "1.8 g of the above chemically sensitized and color sensitized silver iodobromide emulsion,
I will correct it to 1.9gJ.

(49), on page 70, line 14, "color magenta coupler" is corrected to "color magenta coupler."

(50), page 70 of the same, corrects Shinuchi's ``dispersed substance)'' to ``)dispersed substance.''

(51), p. 71, Shinuchi's "amine" is "amino"
I will correct it.

(52), "Ammonium bromide" on page 72, line 15 is corrected to "ammonium bromide."

(53) ``11 and'' on page 73, line 3, rl l
I am corrected.

(54), “Table-15” in the second line of page 80 is changed to “Table-15”.
14” and correct it.

(55), “Table-16” on the second line of page 81 is changed to “Table-16”.
15” and correct it.

(56) On page 81, line 16, "Table 17" is corrected to "Table 16."

(57), "low iodine shell" at the end of page 81 is corrected to "outermost shell."

(58), “Table-18” on page 82, line 4 of the same page is changed to “Table-18”.
17,” I corrected.

(59), on page 82, line 8, ``Capri'' is corrected to ``Kabri,''.

(60) On page 82, line 12, "Table 19" is corrected to "Table 18."

1 and above - (Voluntary) Proceedings September q, 1985 1, Indication of the case 1985 Patent Application No. 86659 2, Title of invention Silver halide photographic light-sensitive material 3, Person making amendment case Relationship with Patent Applicant Address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name
(127) Roku Konishi Photo Industry Co., Ltd. 4, Agent address: FINE Building 6, 2-4-11 Shibasaki-cho, Tachikawa-shi, Tokyo, Number of inventions increased by amendment 7, Detailed explanation of the invention in the specification subject to amendment Column (1), page 11, line 6 of the specification, “ΔIj J”
■” and correct it.

(2), page 43, line 9, r240gJ to r1200
I will correct it as gJ.

(3), Table 5 on page 58 of the same, and table on page 59 of the same
6.

1 or above -

Claims (1)

[Claims] 1 An inner core consisting essentially of silver bromide and/or silver iodobromide, and a plurality of outer shells provided outside this inner core and consisting essentially of silver bromide and/or silver iodobromide. In the silver halide photographic material containing negative-working silver halide grains, the iodine content of the outermost shell of the silver halide grain is 10 mol% or less, and the iodine content of the outermost shell is 6 mol % or less. A shell with a high iodine content higher than mol% is provided inside the outermost shell, and an intermediate shell having an iodine content intermediate between these two shells is provided between the outermost shell and the high iodine content shell, and a silver halide photograph characterized in that the iodine content of the intermediate shell is 3 mol% or more higher than that of the outermost shell, and the iodine content of the high iodine content shell is 3 mol% or more higher than that of the intermediate shell. photosensitive material.