JPH0664309B2 - Silver halide photosensitive material sensitized in the presence of silver halide solvent - Google Patents

Description

Detailed Description of the Invention [Industrial applications]

The present invention relates to a silver halide light-sensitive material in which the presence of a specific silver halide crystal plane and a sensitizing process are designated in the silver halide grains contained in a silver halide emulsion, and the photographic characteristics of the specific crystal plane such as fog and sensitivity. Alternatively, it relates to a silver halide light-sensitive material that exhibits an effect on storage stability.

[Prior art]

In recent years, the demand for silver halide emulsions for photography has become more and more stringent, and higher and higher standards are demanded for photographic performance such as high sensitivity, excellent graininess, high sharpness, low fog density and sufficiently high optical density. Has been done. In response to these requirements, a silver iodobromide emulsion containing 10 mol% or less of silver iodide is well known as a high-sensitivity emulsion. And, as a method for preparing these emulsions, conventionally, pH conditions such as ammonia method, neutral method and acidic method, pAg
As a method for controlling the conditions and a mixing method, a single jet method, a double jet method and the like are known. On the basis of these known techniques, precise technical means have been studied and put into practical use for the purpose of achieving high sensitivity, improvement of graininess, high sharpness and low fog. Especially in silver bromide and silver iodobromide emulsions, emulsions in which not only the crystal habit and the grain size distribution but also the concentration distribution of silver iodide within individual silver halide grains are controlled have been studied. The most orthodox ways to achieve photographic performance such as high sensitivity, excellent graininess, high sharpness, low fog density and high enough covering power as mentioned above are to improve the quantum efficiency of silver halide. That is. For this purpose, knowledge of solid state physics, etc. is being actively incorporated.
A study that theoretically calculated this quantum efficiency and considered the effect of the particle size distribution is, for example, the 1980 Tokyo Symposium proceedings on photographic progress, "Interactions Between Lights and Materials for Photographics".・ Applications ”is described on page 91. According to this research, it is predicted that narrowing the grain size distribution to produce a monodisperse emulsion is effective in improving quantum efficiency. In addition, in a process called chemical sensitization which will be described in detail later for achieving the sensitization of the silver halide emulsion, the monodisperse emulsion is also used in order to efficiently achieve high sensitivity while maintaining low fog. The reasoning that is likely to be advantageous is also considered reasonable. To industrially produce a monodisperse emulsion, JP-A-54-48521
Under the strict control of pAg and pH as described in No. 6, the theoretically required control of the feed rate of silver ions and halogen ions to the reaction system and sufficient stirring conditions are required. The silver halide emulsion produced under these conditions has a cubic, octahedral, or tetrahedral (100) face and (111) face in various proportions.
It consists of so-called normal crystal grains. It is known that such normal crystal grains can increase the sensitivity. On the other hand, a silver iodobromide emulsion comprising polydispersed twin grains has been known as a silver halide emulsion suitable for a high speed photographic film. Further, JP-A-58-113927 and others disclose silver iodobromide emulsions containing flat twinned grains. Although these techniques contribute to high sensitivity, there is a continuing need for techniques that can achieve even higher sensitivity. As a silver halide grain capable of obtaining high sensitivity as a manifestation thereof, Japanese Patent Application No. 59-158111 and JP-A No. 60-222842 disclose silver iodobromide grains having a (110) plane and excellent photographic characteristics. In addition, JP-B-55-42737 discloses a photographic emulsion containing rhombodecahedral silver chlorobromide grains having a (110) face with less fog. On the other hand, Japanese Patent Application No. 59-206765 discloses silver bromide and silver iodobromide grains having a crystal plane having a ridge in the center of the (110) plane, and it is shown that this can further increase the sensitivity. Has been done. This crystal plane is considered to be a very high-order crystal plane, and the Miller index cannot be determined, but its characteristics are described in Japanese Patent Application No. 59-206765, and for convenience,
It is named (110) plane. As described above, the relationship between the crystal planes of silver halide grains and photographic characteristics is extremely deep, and by studying the relationship hidden between them in more detail, a silver halide emulsion showing more excellent characteristics was developed. Have the potential to On the other hand, in the field of chemical sensitization treatment, the chemical sensitization reaction is highly dependent on crystal habit.
Since more sulfur sensitized nuclei are formed on the (111) surface than on the surface, latent image formation becomes dispersive and efficiency is poor, and it is known that sensitization efficiency is poor. It has been considered disadvantageous or difficult to put silver halide grains having a (111) plane into practical use. On the other hand, conventionally, hydroxyazaindene compounds are well known in the art as stabilizers for photographic emulsions because they have the property of suppressing chemical sensitization by sulfur-containing compounds. It is added for the purpose of stopping and / or preventing fogging during the manufacturing process, storage, or development processing. It is also known that this compound has an action of increasing photographic sensitivity. For example, in British Patent No. 1,315,755, as a method for sensitizing a silver halide emulsion (sulfur + gold), azaindene was added before sulfur sensitization, and a monovalent gold complex salt compound containing sulfur was added simultaneously or thereafter. Addition and ripening are described to increase the intrinsic sensitivity of silver halide over conventional methods. Further, in JP-A-50-63914 and German Patent Application (OLS) 2,419,798, after silver sensitizing a monodisperse silver halide grain emulsion of cubic grains having a silver bromide content of 80% or more, It is stated that the inclusion of a hydroxytetrazaindene compound increases the sensitivity. However, in this publication, crystal forms other than cubes, for example, octahedral grains and flat grains substantially in the form of grains surrounded by (111) planes, the sensitivity is rather reduced or slightly increased. It is also described that. Further, JP-A-51-77223 discloses that the average grain size of silver halide grains in a silver halide photographic emulsion subjected to sulfur sensitization is 0.
It is described that when it does not exceed 5 μm, the presence of a certain hydroxytetrazaindene compound in this photographic emulsion increases the sensitivity. However, it is common sense in the art to add a hydroxytetrazaindene compound as a stabilizer after the chemical sensitization treatment regardless of the presence or absence of the sensitizing effect or its recognition. JP-A-50-63914 and 51
-77223 is not expected as a new sensitization method. Further, many patents such as U.S. Pat. No. 3,271,157 disclose a technique of using a silver halide solvent for sensitization. However, the sensitizing treatment with the solvent gives relatively good results to an emulsion composed of grains having a (111) plane, but is still insufficient, and in general, fogging is likely to occur. In the case of silver halide grain emulsions having (100) face, (110) face or (111) face either individually or in combination, there is a defect in systematic countermeasures against illuminance failure due to high illuminance. This is a problem in the present day when the conditions are diverse.

[Object of the Invention]

An object of the present invention is to provide a silver halide photographic light-sensitive material which is effective and stable in chemical sensitization, has low fog, high sensitivity and good storage stability and does not have high illuminance.

[Constitution of the invention]

The above-mentioned object of the present invention is to provide a silver halide photographic light-sensitive material comprising at least one silver halide emulsion,
It is obtained by chemically sensitizing at least one silver halide emulsion layer with silver halide grains having a crystal plane having a ridge in the center of the (110) plane in the presence of at least one silver halide solvent. It is achieved by a silver halide photographic light-sensitive material characterized by containing a silver halide emulsion. Next, the present invention will be described in detail. First, regarding a silver halide grain having a crystal plane having a ridge in the center of the so-called (110) plane according to the present invention, that is, a plane defined by (nn1) (hereinafter simply referred to as (nn1) crystal plane or (nn1) plane) explain. FIG. 1 is a diagram showing the morphology of the entire silver halide crystal when the outer surface is composed of only (nn1) crystal faces. The second
The figure is a side view seen from the direction of the straight line b ₁ b ₂ in FIG. (n
There are 24 equivalent crystal faces represented as n1) crystal faces. For this reason, all outer surfaces are crystals of (nn1) crystal face in the form of a dodecahedron, and each plane forming the outer surface is an obtuse triangle. There are two types of vertices. That is, the equivalent Naru 6 vertices and a ₁ in Fig. 1,
Eight vertices equivalent to b ₁ . Vertex a ₁ 8 plane and is bounded, 3 plan Vertex b ₁ is bounded. There are also two types of edges. That is, side a _{1 in} FIG.
There are 24 sides c ₁ equivalent to b ₁ and 12 sides c ₂ equivalent to side a ₁ a ₂ . Next, the relationship between the (nn1) plane, the (111) plane, and the (110) plane will be described with reference to sectional views. A solid line 1 of FIG. 3 shows a cross-sectional view of the tetrahedron of FIG. 1 on the plane a including the straight line b ₁ b ₂ and perpendicular to the triangle a ₁ a ₂ b ₁ and the triangle a ₁ a ₂ b ₂ . That is, in FIG. 3, the solid line 1 represents the line of intersection between the plane d and the (nn1) plane. On the other hand, the broken line 2 represents the (110) plane and the alternate long and short dash line 3 represents the (111) plane. The directions of the (nn1) plane, the (110) plane and the (111) plane are normal vectors, and Be done. That is p
= [Nn1] (n is a natural number, n ≧ 2), q = [110], r = [111]
It can be expressed as. θ is the value of the two adjoining edges a ₁ a ₂
(nn1) is the angle formed by the crystal plane, where n ≧ 2 and n is 110 ° <θ <180 ° due to the limitation of a natural number. That is, the (nn1) plane intersects with two of the three axes of the crystal at equal distances from the origin, and intersects with the remaining one axis at a slight inclination instead of parallel, so the first is (11 ¹ / _n ). Can be represented
Therefore, it is displayed as (nn1). From the above, it is clear that the (nn1) crystal plane according to the present invention is a crystal plane which is completely different from the (111) crystal plane and the (110) crystal plane which are conventionally known in silver halide microcrystals. Further, it is not necessary to explain the difference from the (100) crystal plane. On the other hand, Japanese Patent Application No. 59-206765 discloses "a crystal plane having a ridge at the center of the (110) plane". In the specification,
This crystal plane is named a quasi (110) plane, and it is described that "the angle between two roof-shaped quasi (110) planes sharing an edge is an obtuse angle than 110 °." That is, the quasi (110) plane is synonymous with the (nn1) crystal plane (n ≧ 2, n is a natural number) according to the present invention. The silver halide grains according to the present invention have all outer surfaces
It need not consist of (nn1) planes. That is, the (111) plane,
The (100) plane or the (110) plane may exist. Examples of these are shown in FIGS. (111) plane and (10
By mixing 0) faces, a 30-sided face (Figs. 4, 5, and 6),
It takes the form of a 38-faced body (Figs. 7, 8, 9) or a 32-sided face (Figs. 10, 11). Further, the silver halide grains having the (nn1) plane according to the present invention may have a uniform internal composition or may have, for example, a core / shell structure having a plurality of composition phases. Further, when a plurality of composition phases form a core / shell structure, the composition phase of the core or shell may be uniform, or the composition may change continuously with each other. One of the most preferable forms is one having a high silver iodide phase deep inside the grain. That is, it is a silver halide grain having a layer (a plurality of layers may be included) having a high silver iodide content or a core deeper in the grain than the grain surface or surface layer. The grain size of the silver halide grains according to the present invention is not particularly limited, and the present invention is effective at least in the range of 0.1 to 3.0 μm. In the present specification, the grain size of silver halide refers to the length of one side of the cube which is equal to the volume. The grain size distribution of the silver halide grains of the emulsion according to the present invention may be monodisperse or polydisperse, or a mixture of these, and can be appropriately selected according to the intended use. The monodispersity is generally expressed by the coefficient of variation (%), which is Is defined as In the silver halide grains of the emulsion according to the present invention, the ratio of the area of the (nn1) plane to the total grain surface area is at least 30% or more, preferably 50% or more, more preferably 70% or more. is there. As described above, the inclusion of silver halide grains having a (nn1) plane in the emulsion makes it possible to prepare a photographic light-sensitive material having high illuminance and less defects, which is excellent in photographic characteristics such as sensitivity, fog and surface quality. The silver halide emulsion according to the present invention can be produced by P. Glafkides by Chimie et Phyeique Photographique.
(Paul Montel, 1967) The F Duffin (GFD
Uffin) Photographic Emulsion Chemistry (The Focal Pr
Published by ess, 1966) Eve El Julikman (VL Zelikma)
n) et al. Making and Coating Phot Emulsion (Making and Coating Phot
It can be prepared using a method described in, for example, ographic Emulsion) (published by The Focal Press, 1964). That is, any of the acidic method, the neutral method, the ammonia method, etc. may be used, and the method of reacting the soluble silver salt with the soluble halogen salt may be a one-sided addition method of adding a silver salt to a mother liquor containing a halide or a mother liquor. Any of a simultaneous mixing method in which a halide and a silver salt solution are added, a combination thereof, or the like may be used. As one form of the simultaneous mixing method, a method of keeping pAg constant in a liquid phase in which silver halide is produced, that is, a so-called controlled double jet method can be used. In the method for producing silver halide grains of the present invention, one of the most preferable modes is a method of adding an aqueous ammoniacal silver nitrate solution and an aqueous halide solution by a controlled double jet method in the presence of ammonia. Furthermore, points to be noted regarding the method for producing a silver halide emulsion containing silver halide grains having a (nn1) plane according to the present invention will be shown. In the present invention, in the step of forming a silver halide grain by mixing a water-soluble silver salt solution and a water-soluble halide solution in the presence of a protective colloid, at least 30 mol% of total silver halide is The pAg of the emulsion produced is 7.0-9.
Control in the range of 8 and during this period, the following general formula (I),
At least one compound selected from the compounds represented by (II), (III) or (IV) and the crystal control compound having a repeating unit represented by the general formula (V) is contained in the above emulsion. Further, after the precipitation of a predetermined amount of silver halide is completed, the period pAg from the time of entering the silver halide grain forming step of adjusting and forming the silver halide grains to the time of entering the desalting step is 7.0 to 9.5.
It is important to control. [Crystal Control Compound] General Formula (I) General formula (II) General formula (III) General formula (IV) General formula (V) In the formula, R ₁ , R ₂ and R ₃ may be the same or different and each is a hydrogen atom, a halogen atom, an amino group, a derivative of an amino group, an alkyl group, a derivative of an alkyl group, an aryl group or a derivative of an aryl group. , A cycloalkyl group, a cycloalkyl group derivative, a mercapto group, a mercapto group derivative or -CONH-R ₄ (R ₄ is a hydrogen atom, an alkyl group, an amino group, an alkyl group derivative, an amino group derivative, a halogen atom, Represents a cycloalkyl group, a cycloalkyl group derivative, an aryl group or an aryl group derivative.)
R ₅ represents a hydrogen atom or an alkyl group,
R ₁ and R ₂ may combine with each other to form a ring (for example, a 5- to 7-membered carbocyclic ring or heterocyclic ring), and X represents the general formula (I), (II),
A monovalent group obtained by removing one hydrogen atom from the compound represented by (III) or (V) (for example, one hydrogen atom from the R _{1 to} R ₃ or OH moieties in the above general formulas (I) to (V)) (Excluded) and J represents a divalent linking group. The tetrazaindene compound represented by the above general formula may be added in advance to the protective colloid solution, gradually added as the silver halide grains grow, or combined. Further, the control of pAg during the period in which at least 30 mol% of the total silver halide is produced is arbitrary as long as it is within the period in which silver halide is produced. Good. Further, this period is preferably a continuous period, but may be intermittent as long as the effect of the present invention is not impaired. PAg during this period is
It is 7.0 to 9.8, preferably 7.3 to 9.5, and more preferably 7.6 to 9.2. And during this period, the pH of the emulsion is 7
It is preferable to keep in the range of -10. PAg of silver halide during this period and outside the grain formation step
Is suitably in the range of 4 to 11.5, preferably in the range of 6 to 11, and the pH is suitably in the range of 2 to 12, preferably in the range of 5 to 11. After obtaining the desired silver halide grains in the silver halide grain forming step, until the desalting step is started,
The pAg must be controlled in the range 7.0-9.5. During this period, the preferred pAg is 7.4 to 9.2, and more preferably
7.8 to 9.0. The pH is preferably 5-8, more preferably 5-7. The time from the end of the particle forming step to the start of the desalting step is within 30 minutes, more preferably within 20 minutes. The silver halide grains of the present invention may be doped with various metal salts or metal complex salts at the time of silver halide precipitation formation, during grain growth or after completion of growth.
For example, gold, platinum, palladium, iridium, rhodium,
Metal salts or complex salts of bismuth, cadmium, copper and the like and combinations thereof can be applied. In a usual use form of the silver halide emulsion according to the present invention, an excess halogen compound generated during the preparation of silver halide grains, or salts or compounds such as nitrates, ammonia and the like, which are by-produced or become unnecessary, are dispersed in the grains. It should be removed (desalting step) from the medium. The removal method is the Nudel water washing method, dialysis method or inorganic salts, anionic surfactant, anionic polymer (eg polystyrene sulfonic acid), or gelatin derivative (eg acylated gelatin, carbamoylated gelatin etc.) commonly used in general emulsions. The precipitation method utilizing coagulation, coagulation precipitation method (flocculation) and the like can be appropriately used. In the method for producing silver halide grains according to the present invention, seed grains may be used, and silver halide may be produced on the surface thereof to grow the grains. When the seed grains are used, the silver halide composition may be within the range capable of forming the silver halide grains according to the present invention. The silver halide grains of the present invention may be used as they are, or may be prepared by blending two or more kinds having different average particle diameters at any time after grain formation to obtain a predetermined gradation. You may use it. In addition, it can be used as a mixture with silver halide grains other than those of the present invention. Next, the general formula (I), (II), (III) or (I
Representative specific examples of the compound represented by V) or the compound having the repeating unit represented by the general formula (V) are shown below. The addition amount of the tetrazaindene compound used in the production of the silver halide grains according to the present invention varies depending on the production conditions such as desired silver halide grain size, emulsion temperature, pH, pAg and silver iodide content. , Per mol of total silver halide produced
The range of 10 ^{−5 to} 2 × 10 ⁻¹ mol is preferable. When the tetrazaindene compound is a compound having a unit represented by the general formula (V), the number of moles of the tetrazaindene portion is the addition amount. The silver halide solvent used in the present invention is (a) described in U.S. Pat.Nos. 3,271,157, 3,531,289, 3,574,628, JP-A-54-1019, 54-158917 and JP-B-58-30571. Organic thioethers, (b) JP-A-53-82408
No. 55-77737 and No. 55-29829, etc., thiourea derivatives described in (c) JP-A No. 53-144319, or a thiocarbonyl sandwiched between a sulfur atom and a nitrogen atom. Compounds having a group, (d) imidazoles described in JP-A-54-100717, (e) sulfite, (f) hydroxyalkyl-substituted ethylenediamines described in JP-A-57-196228, ( g) Substituted mercaptotetrazoles described in JP-A-57-202531, and (h) benzimidazole derivatives described in JP-A-58-54333. Next, specific examples of the silver halide solvents of each of these groups (a) to (h) will be given. (a) Group; (b) Group; (c) Group; (d) Group; (e) Group; (e-1) K ₂ SO ₃ (f) Group; (g) Group; (h) Group; These solvents can be used in combination of two or more.
Preferred solvents include thioethers, thioureas,
Examples thereof include ethylenediamines. These solvents are used in the range of 10 ^{-5 to} 2 mol per mol of silver halide. In the present invention, various chemical sensitizing treatments which are usually used can be used in combination. There are sulfur sensitizers, selenium sensitizers, and tellurium sensitizers as the chalcogen sensitizers used in the chemical sensitization treatment, but sulfur sensitizers and selenium sensitizers are preferable for use in photography. Known sulfur sensitizers can be used. For example, thiosulfur salt, allylthiocarbamide, thiourea, allylisothiocyanate, cystine, p-toluenethiosulfonate, rhodanine and the like can be mentioned. Other U.S. Patents 1,574,944 and 2,410,6
No. 98, No. 2,278,947, No. 2,728,668, No. 3,501,313
No. 3,656,955, West German Application Publication (OLS) 1,422,869,
Sulfur sensitizers described in JP-A Nos. 56-24937 and 55-45016 can also be used. The sulfur sensitizer may be added in an amount sufficient to effectively increase the sensitivity of the emulsion. This amount varies over a considerable range under various conditions such as pH, temperature, and size of silver halide grains, but as a guide, it is about 10 ^-7 mol to about 10 mol per mol of silver halide.
^-1 mol is preferable. Examples of selenium sensitizers include aliphatic isoselenocyanates such as allyl isoselenocyanate, selenoureas, selenoketones, selenoamides, selenocarboxylic acids and esters, selenophosphates, diethyl selenide, and diethyl diselenide. And the like, and specific examples thereof are disclosed in US Pat. No. 1,574,94
4, No. 1,602,592, No. 1,623,499. The addition amount varies over a wide range similarly to the sulfur sensitizer, but as a guide, it is preferably about 10 ^-7 to 10 ^-1 mol per mol of silver halide. In the present invention, as the gold sensitizer, the valence of gold may be +1 or +3, and various gold compounds are used. Typical examples are chloroaurate, potassium chloroaurate,
Autric trichloride, potassium auriothiocyanate, potassium iodoaurate, tetracyano auric acid, ammonium aurothiocyanate,
Pyridyl trichloro gold etc. are mentioned. The amount of the gold sensitizer added varies depending on various conditions, but as a guide, it is preferably in the range of about 10 ^-7 to 10 ^-1 mol per mol of silver halide. The gold sensitizer may be added at the same time as the sulfur sensitizer or the selenium sensitizer, or during or after the sulfur or selenium sensitization step. The pAg of the emulsion to be subjected to sulfur sensitization, selenium sensitization and gold sensitization in the present invention is preferably 5.0 to 10.0 and the pH is preferably 5.0 to 9.0. The chemical sensitization method of the present invention includes other noble metals such as platinum,
A sensitizing method using a metal such as palladium, iridium or rhodium or a salt thereof can be used together. Complexes such as Rh, Pd, Ir and Pt are effective as compounds that release gold ions from gold-gelatinate and promote the adsorption of gold ions on silver halide grains. Specific compounds include (NH ₄ ) ₂ [PtCl ₄ ], (NH ₄ ) ₂ [PdCl ₄ ],
K ₃ [IrBr ₆ ], (NH ₄ ) ₃ [RhCl ₆ ] 12H ₂ O, and the like,
Particularly preferred is ammonium tetrachloropalladium (II) (NH ₄ ) ₂ PdCl ₄ . The addition amount is preferably in the range of 10 to 100 times in stoichiometric ratio (molar ratio) to the gold sensitizer. The time of addition may be any of the steps of starting, in progress, and after completion of the chemical sensitization process, but preferably during the chemical sensitization process, particularly preferably at the same time as or before or after the addition of the gold sensitizer. Is. In the present invention, reduction sensitization can also be used in combination. The reducing agent is not limited, and examples thereof include known stannous chloride, thiourea dioxide, hydrazine derivatives, polyamines and the like. The reduction sensitization is carried out during the growth of silver halide grains, but preferably after the completion of chalcogen sensitization, gold sensitization and noble metal sensitization. Further, in the chemical sensitization treatment, a compound having a nitrogen-containing heterocycle, particularly preferably an azaindene ring may be allowed to coexist. The addition amount of the nitrogen-containing heterocyclic compound varies over a wide range depending on the emulsion size, composition, chemical sensitization conditions, etc., but it is preferable to form a monomolecular layer to 10 molecular layers on the surface of the silver halide grain. It is advisable to add such an amount that This addition amount can be adjusted by controlling the adsorption equilibrium state by changing pH or / and temperature during sensitization. Further, two or more kinds of the above compounds may be added to the emulsion so that the total amount thereof is within the above range. The compound can be added to the emulsion as a solution by dissolving it in an appropriate solvent (for example, water or an aqueous alkali solution) that does not adversely affect the photographic emulsion. The addition time is preferably before or at the same time as the addition of the sulfur sensitizer or the selenium sensitizer for chemical sensitization. The gold sensitizer may be added during or after the sensitization of sulfur or selenium. Further, the silver halide grains can be optically sensitized to a desired wavelength range. The optical sensitizing method of the emulsion of the present invention is not particularly limited, and examples thereof include a cyanine dye such as a zeromethine dye, a monomethine dye, a dimethine dye, and a trimethine dye, or an optical sensitizer such as a merocyanine dye alone or in combination (for example, a supersensitizer). (Color sensitization) Optical sensitization is possible. For these technologies, U.S. Pat.No. 2,688,545,
2,912,329, 3,397,060, 3,615,635, 3,6
28,964, British Patents 1,195,302, 1,242,588, 1,
293,862, West German patent (OLS) 2,030,326, 2,121,780
No. 4, Japanese Patent Publication Nos. 43-4936 and 44-14030. The selection can be arbitrarily determined depending on the wavelength region to be sensitized, sensitivity, etc., according to the purpose and application of the light-sensitive material. As a binder for the silver halide grains according to the present invention or a dispersion medium used for producing the grains, a hydrophilic colloid usually used for silver halide emulsions is used. As the hydrophilic colloid, not only gelatin (either lime treatment or acid treatment may be used) but also gelatin derivatives such as gelatin and aromatic sulfonyl chloride, acid chloride, acid anhydride as described in US Pat. No. 2,614,928. , Gelatin derivatives prepared by reaction with isocyanates and 1,4-dikents, Gelatin derivatives prepared by reaction of gelatin with trimellitic anhydride described in US Pat. No. 3,118,766, Japanese Patent Publication No. 39-5514. Gelatin derivatives by the reaction of an organic acid having the described active halogen with gelatin, gelatin derivatives by the reaction of an aromatic glycidiether with gelatin as described in JP-B-42-26845, and US Pat. No. 3,186,846. Maleimide,
Gelatin derivatives by reaction of maleamic acid, unsaturated aliphatic diamide and the like with gelatin, sulfoalkylated gelatin described in British Patent 1,033,189, US Pat.
Polyoxyalkylene derivatives of gelatin as described in 553; polymeric graft products of gelatin, such as acrylic acid, methacrylic acid, esters thereof with mono- or polyhydric alcohols, also amides, acrylics (or methacrylics) Grafting of ethryl, styrene and other vinyl monomers alone or in combination with gelatin; synthetic hydrophilic polymer substances such as vinyl alcohol, N-vinylpyrrolidone, hydroxyalkyl (meth) acrylate, (meth) acrylamide, N Homopolymers containing monomers such as substituted (meth) acrylamides and N-substituted (meth) acrylamides or copolymers thereof, and copolymers of these with (meth) acrylic acid esters, vinyl acetate, styrene, etc. , Maleic anhydride with any of the above, Such as Reamin acid glue copolymer and the like; natural hydrophilic polymeric substance other than gelatin, such as casein, agar alginate polysaccharides can be used alone or in combination. The emulsion containing silver halide grains according to the present invention can contain various additives usually used depending on the purpose.
Examples of these additives include azaindenes, triazoles, tetrazoles, imidazolium salts, tetrazolium salts, stabilizers and antifoggants such as polyhydroxy compounds; aldehyde-based, aziridine-based, isoxazole-based, vinyl sulfone-based, Acryloyl-based, carbodiimide-based, maleimide-based, methanesulfonate-based, triazine-based hardening agents; benzyl alcohol, polyoxyethylene-based compounds and other development accelerators; chroman-based, coumaran-based, bisphenol-based, phosphites System image stabilizers; waxes, glycerides of higher fatty acids, and lubricants such as higher alcohol esters of higher fatty acids. Further, a coating aid as a surfactant, an agent for improving the permeability to a processing liquid, a defoaming agent or a material for controlling various physical properties of a light-sensitive material,
Various anionic, cationic, nonionic or amphoteric compounds can be used. As the antistatic agent, diacetyl cellulose, a styrene perfluoroalkyl sodium sulphate maleate copolymer, an alkali salt of a reaction product of a styrene-maleic anhydride copolymer and p-aminobenzenesulfonic acid, and the like are effective. Examples of matting agents include methyl polymethacrylate, polystyrene, and alkali-soluble polymers. It is also possible to use colloidal silicon oxide. Examples of latex added to improve the physical properties of the film include copolymers of acrylic acid ester, vinyl ester and the like with other monomers having an ethylene group. Examples of the gelatin plasticizer include glycerin and glycol compounds, and examples of the thickener include styrene-sodium maleate copolymer and alkyl vinyl ether-maleic acid copolymer. The silver halide grain according to the present invention is used for general black and white, X ray, color, infrared, micro, silver dye bleaching method,
It can be effectively applied to photographic light-sensitive materials for various purposes such as reversal and diffusion transfer method. The emulsion having silver halide grains of the present invention can have a rich latitude by mixing at least two types of emulsions having different average grain sizes but different sensitivities, or by coating a plurality of layers. To apply the silver halide grains according to the present invention to a color photographic light-sensitive material, cyan, magenta and yellow are added to an emulsion containing the silver halide grains according to the present invention adjusted to have red-sensitivity, green-sensitivity and blue-sensitivity. The techniques and materials used for the color light-sensitive material, such as inclusion of a coupler in combination, may be applied. As the yellow coupler, a closed ketomethylene type coupler can be used. Among these, benzoylacetanilide compounds and pivaloylacetanilide compounds are useful. Examples of magenta couplers are pyrazolone compounds, indazolone compounds, cyanoacetyl compounds,
As the cyan coupler, a phenol compound, a naphthol compound or the like can be used. In the silver halide photographic light-sensitive material of the present invention, each of the red-sensitive emulsion layer, the green-sensitive emulsion layer and the blue-sensitive emulsion layer is 2
It may be composed of two or more layers. For example, in a color negative photographic light-sensitive material, usually two or three layers are preferably used. The coating position of each emulsion layer can be arbitrarily determined according to the purpose of use. When a plurality of the same color-sensitive layers are used, they can be separately applied. The emulsion layer containing silver halide grains according to the present invention can be applied to any of these photosensitive layers. In addition,
When each color-sensitive layer is composed of two or more layers having different sensitivities, the effect of the present invention is greater when applied to a layer having higher sensitivity than when applied to a layer having lower sensitivity. Examples of the support for the photographic light-sensitive material include baryta paper and
Polyethylene coated paper, polypropylene synthetic paper, glass,
Usually used materials such as cellulose acetate, cellulose nitrate, polyvinyl acetal, polypropylene, polyester films such as polyethylene terephthalate, polystyrene and the like can be appropriately selected according to the purpose of use of the photographic light-sensitive material. These supports are subjected to a subbing process, if necessary. The photographic light-sensitive material having silver halide grains according to the present invention can be subjected to development processing after exposure by a known method usually used. The black-and-white developing solution is an alkaline solution containing a developing agent such as hydroxybenzenes, aminophenols, aminobenzenes, and other alkali metal sulfites, carbonates,
It may contain bisulfite, bromide, iodide and the like. Further, when the photographic light-sensitive material is for color, color development can be carried out by a commonly used color development method. In the reversal method, first, development is carried out with a black-and-white negative developing solution, then white exposure is carried out or processing is carried out in a bath containing a fogging agent, and then color development is carried out with an alkaline developing solution containing a color developing agent.
There is no particular limitation on the treatment method, and any treatment method can be applied, for example, as a typical one,
After color development, apply bleach-fixing treatment, and then wash and stabilize treatment if necessary, or after color development, apply bleaching and fixing treatment separately, and then wash and stabilize treatment as needed. You can

【Example】

Next, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. Example 1 Emulsions EM-1 and (11) containing grains having (nn1) planes were prepared by the following method.
Emulsion EM-2 of 1) side was prepared. Preparation of EM-1: EM-1 consists of core / shell type silver iodobromide grains having a high silver iodide core therein, the grains comprising:
It is a nearly perfect dodecahedron consisting of (nn1) planes with a grain size of 1.0 μm. The preparation method was as follows: gelatin at 4 ° C and pAg 8.6
-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (hereinafter referred to as TAI) was added to a mother liquor containing a 0.25 μm silver iodobromide seed emulsion and an aqueous solution of ammonium nitrate silver nitrate and bromide. It was prepared by adding a mixed aqueous solution of potassium, potassium iodide and gelatin by the controlled double jet method at a critical rate at which new crystal nuclei were not generated. The mixing ratio of potassium iodide and potassium bromide was changed according to the change in particle size. That is, when the calculated particle size is up to 0.65 μm, the molar ratio of potassium iodide to the total potassium halide is 15 mol%, and when the particle size is 0.65 μm to 0.80 μm, 5 mol%,
It was set to 0.3 mol% between 0.80 μm and 1.0 μm. : Preparation of EM-2: Consists of core / shell type silver iodobromide grains having a high silver iodide core inside as in EM-1, and the grains consist of (111) faces of 1.0 μm in grain size. It is a nearly perfect octahedron. The preparation method is as follows: a mother liquor containing a silver iodobromide seed emulsion of 0.15 μm (silver iodide content 4 mol%) in the presence of gelatin TAI at 40 ° C. and pAg8.6, an aqueous solution of ammoniacal silver nitrate, and an odor. Further, a mixed aqueous solution of potassium iodide, potassium iodide and gelatin is added by the controlled double jet method at a maximum addition rate that maintains a solubility product [Ag ⁺ ] [X ⁻ ] at which new crystal nuclei are not generated, thereby further forming grains. The PAg was continuously changed from 9 to 10, and the amount of TAI was changed. At this time, the molar ratio of potassium iodide to the added silver nitrate was 4 mol%. Next, a predetermined amount of the silver halide solvent according to the present invention was added to each of the above emulsions, sodium thiosulfate and chloroauric acid were further added, and chemical ripening was performed at 55 ° C. for 60 minutes. . Next, TAI was added to each emulsion to stabilize it, and after adding general photographic additives such as a spreader and a hardener, the amount of Ag was 50 mg / d on the subbed polyethylene terephthalate film.
Sample Nos. 1 to 10 were prepared by coating and drying so as to be m ² . Sensitometry of these samples was performed as follows.
The exposure is a tungsten bulb as a light source (color density 5,400 °
K) was used for a 1/50 second exposure through an optical wedge and a 10 ^-6 second exposure with a xenon flash. The development was performed using a roller-conveying type automatic development according to the following steps. Processing temperature Processing time Development 35 ° C 25 seconds Fixing 34 ° C 25 seconds Washing with water 33 ° C 25 seconds Drying 45 ° C 15 seconds The composition of the developer used is as follows. Anhydrous sodium sulfite 70g Hydroquinone 10g Anhydrous acid 1g Sodium carbonate-hydrate 20g 1-Phenyl-3-pyrazolidone 0.35g Sodium hydroxide 5g 5-Methyl-benzotriazole 0.05g Potassium bromide 5g Glutaraldehyde bisulfite 15g Glacial acetic acid 8g Water Add to finish 1. The results of sensitometry are shown in Table 1. Sensitivity is 1/50 second exposure sensitivity of emulsion EM-1 without adding silver halide solvent
The relative sensitivity was expressed as 100. As is clear from Table 1, sample Nos. 2 to 4 obtained by the method of the present invention show less increase in fog than the comparative sample. In addition, the 1/50 second exposure sensitivity and the 10 ^-6 exposure sensitivity are high, and it can be seen that the high illuminance failure is small. Example-2 For each of the emulsions EM-1 and EM-2 obtained in Example-1,
As shown in Table 2, the silver halide solvent of the present invention was added in a predetermined amount, and further the sensitizing dye anhydro-3,3'-di- (3-sulfopropyl) -5,5'-dichloro-9 was added. −
Ethyl-thiacarbocyanine hydroxide, sodium thiosulfate and chloroauric acid were added, and the mixture was aged at 55 ° C for 60 minutes,
It was spectrally and chemically sensitized. After stabilizing these emulsions by adding TAI and 1-phenyl-5-mercaptotetrazole, and further adding the following coupler dispersions, other commonly used extenders, hardeners and other photographic additives, Sample No. 10 was prepared by coating silver on a triacetate base so that the amount of silver was 20 mg / dm ^2.
~ 20 created. Coupler dispersion hydroxy-N- {γ-2,4-di-tert
-Amylphenoxypropyl)}-2-naphthamide
80 g was completely dissolved in a mixed solution of 100 m of tricresyl phosphate and 50 m of ethyl acetate, and 2 g of sorbitan monolaurate was further added. 1 kg of 10% by weight gelatin aqueous solution containing 2.5 g of dodecylbenzene sulfonic acid
It was added to the inside, stirred at high speed, and further subjected to ultrasonic stirring to be emulsified and dispersed. The above sample was subjected to the same wedge exposure as in Example-1, and then color development was performed at 38 ° C. for 3 minutes using a color developing solution having the following composition. Color developer composition 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) -aniline sulfate 4.80 g anhydrous sodium sulfite 0.14 g hydroxylamine 1/2 sulfate 1.98 g sulfuric acid 0.74 g anhydrous carbonic acid Potassium 28.85 g Anhydrous potassium hydrogen carbonate 3.46 g Anhydrous potassium sulfite 5.10 g Potassium bromide 1.16 g Sodium chloride 0.14 g Nitrilotriacetic acid trisodium salt (monohydrate) 1.20 g Potassium hydroxide 1.48 g Add water to make 1. The results of sensitometry are shown in Table 2. Sensitivity is 1/50 second exposure sensitivity of emulsion EM-1 without adding silver halide solvent
It was expressed as relative sensitivity as 100. As is clear from Table 2, sample Nos. 10 to 12 obtained by the method of the present invention show less increase in fog than the comparative sample. Also, the exposure sensitivity of 1/50 second and the exposure sensitivity of 10 ^-6 seconds are high, and it can be seen that the high illumination failure is small.

[Brief description of drawings]

FIG. 1, FIG. 2 and FIG. 3 are schematic explanatory views of the (nn1) plane according to the present invention. 1 …… (nn1) plane 2 …… (110) plane 3 …… (111) plane a and b… Vertex c… Ridge line formed by the intersecting line of two (nn1) planes overlapping the (110) plane

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References Japanese Patent Publication 4-31378 (JP, B2)

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material comprising at least one silver halide emulsion, wherein at least one silver halide emulsion layer has a crystal having a ridge at the center of the (110) plane. A silver halide light-sensitive material comprising a silver halide emulsion obtained by chemically sensitizing a surface-containing silver halide grain in the presence of at least one silver halide solvent.