JPS62178235A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent the hindrance of chemical sensitization by gold-gelatinate by chemically sensitizing silver iodobromide core/shell type silver halide particles having a (110) face in the presence of >=1 kinds among a chalcogen sensitizer, gold sensitizer and noble metallic compd. CONSTITUTION:The noble metallic compd. is the compd. expressed by the general formula R2MX4 or R3M'X6 (where R is a hydrogen atom, ammonium group or alkali metal atom, M is Pt or Pd, M' is Zr or Rh, X is a halogen atom). The noble metallic compd. is incorporated preferably at 10-100mol per mol of the gold sensitizer and is particularly preferably chemically sensitized in the presence of a Pd compd. The effect of the noble metallic compd. is remarkably provided with good reproducibility to the silver halide particles of the core/shell type having the (110) face by the above-mentioned constitution. A photosensitive material which is low in fogging while having high sensitivity and has an excellent shelf life and thermal stability is thus obtd.

Description

[Detailed description of the invention] [Industrial application field]

The present invention relates to a silver halide photographic light-sensitive material with improved JT characteristics, and more particularly to a silver halide photographic light-sensitive material which prevents capri, achieves high sensitivity, and has excellent storage stability.

[Conventional technology]

In recent years, demands on silver halide photographic light-sensitive materials (hereinafter simply referred to as light-sensitive materials) have become increasingly strict, and there is a strong demand for the development of light-sensitive materials with particularly high sensitivity and excellent image characteristics. Conventionally, highly sensitive silver halide emulsions are obtained. For this reason, silver halide emulsions with different silver halide compositions inside and near the surface of silver halide grains have been used in practice. More monodisperse? By using cutting, quantum efficiency is improved,
It is now possible to obtain emulsions with high sensitivity and low fog, and it is now expected that in the chemical sensitization process, sensitization can be efficiently achieved while maintaining a low degree of fog. However, in reality, when chemical sensitization is applied to these high-sensitivity emulsions, it is difficult to control, and not only low fog and high sensitivity cannot be achieved as expected, but also unfavorable results in terms of shelf life can be obtained. There are many. One of the reasons for this is money.
There is a gelatin complex. In other words, the gold ion of a gold sensitizer commonly used as a chemical sensitizer has 215 forms with gelatin (gold-gelatinate).
4+n is formed and captured in gelatin, making it difficult to control chemical sensitization, and the captured gold ions have a negative effect on the preservation of photosensitive materials. Improvements to these problems For this reason, Japanese Patent Application No. 59-191362 discloses Rl+, Ir,
Although storage stability has been improved by chemically ripening in the presence of Pd or Pt, it has not yet reached a satisfactory level. In addition, the efficiency of noble metal compounds belonging to Group I of the periodic table on silver halide grains having (110) planes was shown in Japanese Patent Application Laid-Open No. 60-222.
No. 842, however, it is unknown for emulsions consisting of core/shell type silver halide grains having a (110) structure in which the intragrain behavior of photoelectrons is very different. The core/shell type silver halide grains having (110) planes are described in detail in Japanese Patent Application No. 59-211764.

[Purpose of the invention]

The purpose of the present invention is to solve the above-mentioned inhibition of chemical sensitization by gold-gelatinate, to achieve stable control of chemical sensitization, and to provide a photosensitive material that has high sensitivity, low fog, and excellent storage stability, especially thermal stability. It's about doing.

[Structure of the invention]

As a result of repeated studies for the above-mentioned purpose, the present inventors have discovered a method for producing a photosensitive material with high sensitivity, low fog, and excellent storage stability in a far more stable manner than in the past. That is, in a silver halide photographic light-sensitive material having a silver halide emulsion layer of at least 1/r7 on a support, the silver halide emulsion layer has at least Iff (but the silver iodide content is lower than that near the surface). Silver iodobromide core/shell type silver halide grains having substantially different (110) planes are treated with a chalcogen sensitizer, a gold sensitizer and an fJ metal compound (RI++Pd,
at least one complex salt of a metal of group Ⅰ of the periodic table such as Pt
The objects of the present invention can be achieved by a silver halide photographic material containing a silver halide emulsion obtained by chemical sensitization in the presence of seeds. In a preferred embodiment of the present invention, the noble metal compound is a compound represented by the following general formula (1) or (2), where R is a hydrogen atom, and ammonium is a compound represented by the general formula (1) or (2).
R2MX. General formula (2) R, M'X. group or alkali metal atom, M is Pt or Pd
, M' is Jr or Rl+. X is a halogen atom. Furthermore, the amount of the metal compound mentioned above is 10 to 1 per mole of the gold sensitizer.
00 mol, and it is preferable to use a Pd compound and/or an Ir compound as the t'1 metal compound, and it is preferable to first chemically sensitize the compound in the presence of a Pt1 compound. According to the configuration of the present invention, a core/shell type (I 1.
O) The effect of the die ash compound can be significantly and reproducibly reduced on the silver halide grains having the plane, and the storage stability and
In particular, stability against heat is significantly improved. Next, the present invention will be explained in detail. The silver halide grains according to the present invention have a Miller index (+10
) has a crystal plane defined as the external face, and consists essentially of silver bromide, iodine, and silver oxide. In addition to the (110) plane, the particle surface has (+00) plane, (
Ill) planes etc. may be present, but the ratio of (+10) planes to the total surface Fn is preferably 20% or more, particularly preferably 80% or more. Furthermore, the presence of (110) planes and their proportion can be determined by a method using an electron microscope or a color absorption dyeing method. The silver halide milk layer of the present invention preferably contains silver halide grains having (1↑0) planes in an amount of 3 (h) of 1% or more, more preferably 50+ut% or more. In the composition of the silver halide grains related to the above, the term "substantially consisting of silver bromide or silver iodobromide" means that silver T other than silver bromide and silver iodide is included within the range that does not impair the effects of the present invention.
It means that it may contain silver monogonide, for example, silver chloride. Specifically, in the case of silver chloride, the ratio should be 5 mol% or less! The amount is preferably 1 mole or less, and more preferably 1 mole or less. The silver iodide ratio C of the silver halide grains according to the present invention is:
Preferably 0 to 40 mol%, 0 to 20 mol! Which range is more preferable, and a range of 0 to 15 mol% is particularly preferable. The silver halide grains according to the present invention are core/shell type silver halide grains comprising a plurality of layers or phases having different silver halide compositions, for example, a core and a plurality of shell layers. The halo:I silver oxide 1rL composition inside the plural-phase grains may contain silver chloride, silver bromide, and the like. Further, the silver halide composition may be uniform within each river, or may change continuously to other phases. A preferable form of the silver halide according to the present invention is one having a high iodine phase inside the grains. That is, it is a silver halide grain that has a shell (or shells) or a core inside the grain, which has a higher normal content than the normal content on the surface of the grain. There is no particular restriction on the particle size of the silver halide grains according to the present invention, and the present invention is at least effective within the range of preferably 0.1 to 3.0 μm layer. In addition, in this Moe lay, the grain size of silver halide is expressed by the height of one side of a cube equal to its volume. The silver halide grains according to the present invention are usually produced and used in a form dispersed in a dispersion medium such as gelatin, that is, in a form called an emulsion. The particle size distribution of the group of particles at this time may be monodisperse, polydisperse, or a mixture of these distributions, and can be appropriately selected depending on the desirability and the like. As in the present invention, by using a silver halide photograph 7L 11 containing silver halide grains whose grain surfaces have a (+10) crystal plane and are substantially made of silver bromide or silver iodobromide, the conventional (+10) It has become possible to obtain various benefits for emulsification that could not be obtained with silver bromide emulsions or iodobromide ff1vL emulsions that do not have crystal planes. For example, ■ Silver bromide emulsion or silver iodobromide with (+11) and/or (ioo) faces? Fog can be suppressed compared to grinding. ■ Silver bromide emulsion or silver iodobromide that has (11,1) plane and/or (+00) plane but does not contain 110) plane? 'L
Higher sensitivity can be obtained compared to 7M. (2) It has a completely different spectral sensitization ability from silver halide emulsions having (111) planes and/or (1,00) planes. For example, the spectral sensitivity spectrum upon spectral sensitization can be made rectangular. Therefore, color reproducibility is significantly improved,
You can make sushi with greatly improved prevention of color mixing. (2) Spectral sensitivity Since the spectrum is made rectangular, stable exposure can be performed even in extreme conditions using LEDs (light emitting diodes) whose wavelengths shift easily depending on the environmental temperature. In order to produce silver halide grains having (110) planes according to the present invention, the method disclosed in Japanese Patent Application Laid-Open No. 60-222842 or Japanese Patent Application No. 158111-1988 can be used. That is, in JP-A-60-222842, in a method for producing a silver halide photographic emulsion in which the surface of silver halide grains consists essentially of silver bromide or silver iodobromide, hydrophilic protective colloid and (11(1) ) Silver halide grains are grown in an aqueous medium containing a compound that promotes the development of crystal planes. It has been shown that it is possible to produce silver halide grains that strike. (+10) A clear chemical classification of substances that promote the development of crystal planes (referred to as son crystal control compounds) is not possible at all, but specifically mercaptoazoles are preferred, especially mercaptotetrazoles and mercaptothiadiazoles. Preferably. Specifically, compounds represented by the following general formulas (1) to (V) are preferred. It does not represent an aryl group (total carbon number 20 or less) or a heterocyclic group that may be substituted. Represents a kill group (total carbon number 12 or more). J-6 represents an optionally substituted amino group (total carbon number of 10 or more F) or an optionally substituted aryl group (total carbon number of IO or less). In the formula, Rh and Re are optionally substituted alkyl groups (
10 or less) or an optionally substituted amino group. The crystal control compounds (1) to (V) may be added at any time until the formation of silver halide grains is completed +iij (including before the completion of Ostwald ripening). Here, the period of grain formation includes the period from the start of addition of silver ions and halogen ions until the time when new crystal nuclei are substantially no longer generated (nucleation period), and the period after which new crystal nuclei are substantially no longer generated. There is a period during which particles grow without being generated (particle growth period). Preferably,

[Added 4° during the growth of J-silver-genide grains. In particular, after the completion of nucleation (nucleation), the completion of particle growth +i
It is preferable to add crystal control compounds (+) to (V) to ij in order to limit the formation of polyparticles. Conversely, it is preferable to use the crystal control compounds (1) to (V) during nucleation or during +iIJ since it is possible to prepare silver halide grains consisting of fine -r grains. The crystal control compounds (1) to (V) may be present in the reaction vessel in advance, or may be added after the start of precipitation. At this time, it may be added directly, or water,
A]'4 It may be added as a solution consisting of a solvent such as a solvent (for example, methanol, ethanol, etc.). Further, the crystal control compounds (1) to (V) may be added to the reaction vessel alone, or may be added to the reaction vessel together with an ice supply solution (for example, a silver nitrate aqueous solution) or a halogen supply solution (for example, a halide aqueous solution). It may be added to. When adding the crystal control compounds (1) to (V), they may be added continuously or intermittently. If the Ia of the crystal control compound of the present invention is increased (for example, by increasing the amount of solution added or increasing the concentration) in accordance with the increase in the surface area of silver halide grains, crystal planes can be effectively controlled. 1- is preferred. The silver halide grains having (110) of the present invention have (+
10) Regarding the proportion of crystal control compound (1
) to (V), the ratio can be easily changed by 4 degrees. For example, as the amount of added crystal control compounds (1) to (V) increases (110
) surface ratio increases, and in the region of additions i and l described later, (
The ratio of (110) to (+10) increases when the amount of the crystal control compound added exceeds the range described below. The amount of the crystal control compounds (1) to (V) to be added varies depending on various conditions such as the type of crystal compound used, the emulsion manufacturing conditions, the composition of the emulsion, the particle size, etc. 1
It is preferably from 5.times.10.sup.-5 to 5.times.10.sup.mol, more preferably from 1.times.10.sup.-' to 1.times.10-' mol, and particularly preferably from 3.times.10-' to 6.times.10-3 mol per mol of silver 0-genide. On the other hand, Tokukai 1 II 59-151! No. III contains (11
0) As a method for producing silver bromide or silver iodobromide grains with self-sided surfaces, a water-soluble silver salt solution and a water-soluble halide solution are mixed in the presence of a protective code [lr]. In the step of forming silver halide, the period during which at least 30 mol% of the total silver halide is produced, I) Ag of the emulsion is 8.0
-95, and during this period, as a crystal control compound, general formula (Vl), (■), (■) or (I
A method is disclosed which is characterized in that at least one compound selected from the compound represented by X) and the compound having a repeating center represented by general formula (X) is incorporated into the emulsion. General formula (■) General formula (IX) General formula (X) I5 ■ Ball C8, -C soup■ In the formula, R, , R, 2 and RIff may be the same or different, and each represents a hydrogen atom and a halogen atom. , amino group, derivative of amino group, alkyl group, derivative of alkyl group, aryl group, derivative of aryl group, cycloalkyl group, derivative of cycloalkyl group, mercapto group, derivative of mercapto group or -CONH-R,, ( R represents a hydrogen atom, an alkyl group, an amino group, a derivative of an alkyl group, a derivative of an amino group, a halogen atom, a cycloalkyl group, a derivative of a cycloalkyl group, an aryl group, or a derivative of an aryl group.) , rt+s represents a hydrogen atom or an alkyl group, rL++ and R+t may be combined to form a ring (e.g., 5- to 7-membered carbocycle, heterocycle), and X is a general formula (Vl), A monovalent]l obtained by removing one hydrogen atom from a compound represented by (■), (■) or (IX) (for example, the general formula (Vl) or IX
) in which one hydrogen atom is removed from the 011 moiety), and J represents a divalent connecting group. In addition to t of crystal control compounds (Vl) to (X) in this manufacturing method, manufacturing conditions such as desired silver halide grain size, emulsion temperature, pH, l)Ag, silver iodide content, etc. Although it varies depending on the
A range of -5 to 2XIO-' moles is preferred. In addition, when the tetrazaindene compound is a compound represented by the general formula (X) and has a distal position, the amount of addition is defined as the number of moles of tetrazaindene 11<min. Methods for adding the crystal control compounds (Vl) to (X) include a method in which they are added in advance to a protective colloid solution, a method in which they are added gradually as silver halide grains grow, and a method in which these are added in combination. In this production method, grains may be grown by using seed grains and producing silver halide on their surfaces. When seed grains are used, their silver halide composition may be within a range capable of forming silver halide grains according to the present invention. The period for controlling the pAg is arbitrary as long as it is within the period during which silver halide is produced, and may be at the beginning, intermediate coating, or end of the silver halide production process. Further, although this period is preferably a continuous period, it may be intermittent as long as the effect of the present invention is not impaired. The pAg during this period is preferably 8.0 to 95, more preferably 8.4 to 9.2. And during this period, the emulsion I)
It is preferable to keep H in the range of 7 to 10. The pAg of silver halide outside this period is suitably in the range of 4 to 11.5, preferably in the range of 6 to 11, and the pH is in the range of 2 to 1.
A range of 2 is suitable, preferably a range of 5 to 11. In this production method, the step of forming silver halide grains for producing silver halide is preferably performed by adding an ammoniacal silver nitrate aqueous solution and a halide aqueous solution by a double jet method in the presence of ammonia. Also,
During this grain growth process, it is preferable to add a silver and halide solution to prevent the generation of new crystal nuclei. The feature of this manufacturing method is that it can provide a silver halide emulsion with excellent monodispersity, as described in Japanese Patent Application No. 59-158111. The outline of the method for producing silver halide grains having (IIG) planes according to the present invention has been described above.
No. 222842 and Japanese Patent Application No. 59-158111. The silver halide grains having (110) planes according to the present invention are produced by cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or a complex salt thereof, rhodium salt or its complex salt, in the process of silver halide grain formation or physical ripening. Complex salts, iron salts, iron complex salts, gold salts, total complex salts, etc. may be present. Further, the amount of these additives may be small or large depending on the intended photosensitive material. Remove soluble salts from emulsion after precipitation or physical ripening! For rice, the Tardel water washing method, which is performed by gelatinizing gelatin, may be used, and inorganic salts, anionic surfactants, anionic polymers (e.g., polystyrene sulfonic acid), or gelatin derivatives (e.g., annated gelatin, carbamoylated A sedimentation method (flocculation method) using gelatin, etc.) may also be used. The core/shell type silver halide grains according to the present invention have a grain structure composed of two or more layers having different silver iodide contents, and have a grain structure composed of two or more layers having different silver iodide contents. It is preferable that the silver iodide content near the surface of the layers is lower than that inside. Here, the term "near the surface" means that the thickness from the surface is 0.01 to 0.
This refers to the 3 μm portion. It is preferable that the difference between the silver iodide content near the surface and inside the surface is 1 mol % or more. In the present invention, the silver iodide content near the surface is preferably as low as possible, and preferably consists essentially of silver bromide. Emulsions containing such silver halide grains have high sensitization efficiency and are particularly suitable for obtaining surface latent image type emulsions. In the core/shell type silver halide grains of the present invention, the slope due to the difference in content from a layer with a high silver iodide content to a layer with a low silver iodide content may have a sharp boundary, and The boundary may be continuously changing and not necessarily obvious. The distribution state of silver iodide in the above silver halide grains is as follows:
It can be detected by various physical measurement methods, and can also be investigated by measuring luminescence at low temperatures as described in the Abstracts of the 7th Annual Conference of the Photographic Society of Japan, 1982. A preferred embodiment of the silver halide grains of the present invention is a silver halide grain containing 0 to 4 mol % of silver iodide near the surface of the grain, and 2 to 15 mol % of silver iodide inside the grain. It is to be. The silver halide emulsion having core/shell type silver halide grains of the present invention may be produced by using monodisperse silver halide grains as a core and coating the core with a layer. In order to produce the core monodisperse silver halide grains, grains of a desired size can be obtained by a double jet method while keeping the pAg constant. For example, a monodisperse silver halide emulsion is , the method described in Japanese Unexamined Patent Publication No. 54-48521 can be applied. For example, it is produced by a method in which an aqueous potassium gelatin solution and an ammoniacal silver nitrate aqueous solution are added to an aqueous gelatin solution containing silver halide seed particles while changing the addition rate as a function of time. In this case, the time function of the addition rate, p
) [, pAg%, temperature, etc., it is possible to obtain highly monodisperse silver halide grains. Regarding the method for producing the above-mentioned core/shell type silver halide grains, for example, West German Patent No. 1,169.290, British Patent No. 1.027,146, JP-A-57-154232
Reference can be made to the descriptions in Japanese Patent Publication No. 51-1417, etc. The chalcogen sensitizer in the present invention is a general term for sulfur sensitizers, selenium sensitizers, and tellurium sensitizers, and sulfur sensitizers and selenium sensitizers are preferred for use in photography. As the sulfur sensitizer, known sulfur sensitizers can be used. Examples include thiosulfate, allylthiocarbamide, thiourea, allyl isothiocyanate, insuti 7, p-toluenethiosulfonate, rhodanine, and the like. Others: U.S. Patent No. 1,574°944, U.S. Patent No. 2.410,6
No. 89, No. 2,278,947, No. 2,728゜66
No. 8, No. 3.501,313, No. 3.656.955
Sulfur sensitizers described in OLS No. 1.422,869, JP-A-56-24937, JP-A-55-45016, etc. can be used. The amount of sulfur sensitizer added may be sufficient to effectively increase the sensitivity of the emulsion. This 1 varies over a considerable range under various conditions such as the amount of nitrogen-containing heterocyclic compound added, I) H1 temperature, and the size of silver halide grains, but as a guide, 1 mol of silver halide About 10-7 mol to about 10-' mol per unit is preferred. Selenium sensitizers can be used instead of sulfur sensitizers, and examples of selenium sensitizers include aliphatic isoselenocyanates such as allyl isoselenocyanate, selenourochords, selenoketones, sele, and noamides. , selenocarphonic acids and esters, selenophosphates, and selenides such as noethylselenide and diethyldiselenide, specific examples of which are described in U.S. Pat.
, No. 574.944, No. 1.602.592, No. 1.
No. 623.499. As with the sulfur sensitizer, the amount added varies over a wide range, but as a guide, approximately 10-
It is preferably about 7 mol to io-' mol. In the present invention, various gold compounds are used as the gold sensitizer, and the valence of gold may be +1 or +3. Typical examples are chloroaurate, potassium chloroaurate,
Auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyanoauric acid, ammonium aurothionoanate,
Examples include pyridyltrichlorogold. The addition of gold sensitizer 1 varies depending on various conditions, but as a guide, it is from about 10-7 mol to lo-7 mol per mol of silver halide.
A range of up to 1 mol is preferred. The gold ions are separated from the gold-gelatinate, and
Preferred compounds that promote adsorption of gold ions onto silver germide grains are those represented by general formula (1) or (n) of OfI.
Complex salts such as R h, P ci, r r, and P L represented by these are effective. Specific compounds include (Nl14)zPL(J), 4.
(Ni14)tPdcL, K, IrBrn, (N
+1. ) JhC(,, 121120, etc.),
Particularly preferred is ammonium tetrachloropalladate(11) (NIl)tPdc(!4).The amount added is 10 to 10 in terms of chemical hl theoretical ratio (molar ratio) to the gold sensitizer.
A range of 0 times is preferred. The addition timing may be at the start of chemical sensitization, during its progress, or after the end of chemical sensitization, but preferably during chemical sensitization,
Particularly preferably simultaneously with the addition of all sensitizers or +i thereof.
Q Later. In the present invention, reduction sensitization can also be used in combination. There are no particular limitations on the reducing agent, but known examples include stannous chloride, dioxychloride, hydrazine derivatives, and polyamines. Reduction sensitization is performed during the growth of silver halide grains, but chalcogen sensitization, gold sensitization and 1th, P
It is preferable to carry out the sensitization after completion of sensitization using a compound selected from noble metal compounds such as d, lr, and PL. Further, the silver halide grains used in the present invention can be chemically sensitized in the presence of a silver halide solvent, so that high sensitivity can be easily achieved. Examples of silver halide solvents used in the present invention include U.S. Pat.
(a)(-
T-machine thioethers, JP-A-53-82408, l1
(b) Diurechord derivatives described in No. i55-77737, No. 55-2982, etc., JP-A-53-1443]9
(c) a silver halide solvent having a thiocarbonyl group sandwiched between an oxygen or sulfur fragment f and a nitrogen atom, (d) imidazoles described in JP-A-54-100717; G) 41i sulfate, (r)dionane-1, and the like. These specific compounds are shown below. (a) +10(C11t)! 5(C11,)2S(C11,)
2011(e) K*5Os (D N)1. SCN, KSCN Particularly preferred solvents include thiocyanate and tetramethylthiourea. Although the amount of the solvent used varies depending on the type, for example, in the case of thiocyanate, m is preferably in the range of 5 mg to 1 g per mole of silver halide. The silver halide emulsion in the present invention can be spectrally sensitized using various dyes. Dyes used include polymethine dyes, including monoanine, merocyanine, complexanine and complex merocyanine (i.e. tri-, tetra- and polynuclear cyanine and merocyanine), oxonol, hemioxonol, styryl, merostyryl and streptonanine. It will be done. Cyanine sensitizing dyes include quinolinium, pyridinium,
Isoquinolium, 3H-indolium, benz(e)indolium, oxacillium, oxazolinium, thiazolium, thiazolinium, selenazolium, selenacylinium, imidazolium, imidazolinium, benzoxacillinium, benzothiazolium, benzoselenazolium, Benzimidazolium, naphthoxazolium,
Included are two basic heterocyclic nuclei linked by a methine linkage, such as derived from naphthothiazolium, naphthoselenazolium, nohydronaphthothiazolium, biryllium and imidazopyrazinium quaternary salts. Merocyanine sensitizing dyes include barbylic acid, 2-thiobarbylic acid, rhodanine, hydantoin, 2-thiohydantoin, 4-thiohydantoin, 2-pyrazolin-5-one, 2-isoxazolin-5-one, indan-1,3 -dione, cyclohexane-1,3-dione,
1,3-dioxane-4,6-dione, pyrazoline-3
, 5-dione, pentane-2,4-dione, alkylsulfonylacetonitrile, malononitrile, isoquinolin-4-one and chroman-2,4-dione with acidic nuclei and basic heterocyclic nuclei of the cyanine dye type. and are linked by a methine bond. Sensitizing dyes useful for sensitizing silver halide emulsions are disclosed in British Patent No. 742.112 and US Pat. No. 1,846.300.
No. 846.3Q1, No. 1,846,302, No. 1.846,303, No. 1,846,304,
2,078.233, 2.089,729, 2,165.338, 2,213,238, 2
, No. 231,658, No. 2,493,747, No. 2,
No. 493,748, No. 2,526.632, No. 2,7
No. 89,964 (Reissued Patent No. 24,292), No. 2,
No. 118.823, No. 2,917,516, No. 3,3
No. 52,857, No. 3,411.916, No. 3,43
No. 1,111, No. 2.295.276, No. 2,481
, No. 898, No. 2.503,776, No. 2.688.
No. 545, No. 2,704,714, No. 2,921,0
No. 67, No. 2,945,763, No. 3,282.93
No. 3, No. 3,397,060, No. 3,660,102
No. 3,660,103, No. 3,335,010, No. 3,352,680, No. 3,384.486,
Same No. 3,397.981, No. 3.4HJ78, Same: a
, No. 623.881, No. 3.718,470, and No. 4.825.349. Examples of useful dye combinations, including supersensitizing dye combinations, are provided in U.S. Pat.
, 506,443 and 3,672,898. An example of a supersensitizing combination consisting of a sensitizing dye and a non-light absorbing additive is U.S. Pat.
thiocyanates in the process of spectral sensitization as shown in U.S. Pat. 3.45 using sulfonated aromatic compounds as shown in U.S. Pat.
7.078, using mercapto-substituted heterocyclic compounds, iodides as shown in British Patent No. 1,413.826, and Gilman (
Other compounds may be used, including those described in the Review of the Mechanisms of Supersensitization (J. Qilman). The process may be carried out at the beginning, during or after the chemical sensitization (called chemical ripening) of the silver germide emulsion, or at an appropriate time prior to coating the emulsion.In addition, a sensitizing dye may be added to the photographic emulsion. As a way to do this,
Various methods proposed in the past can be applied. For example, as described in U.S. Pat. No. 3,469,987, a sensitizing dye may be dissolved in a commercially available organic solvent, the solution may be dispersed in a hydrophilic colloid, and this dispersion may be added to an emulsion. good. The sensitizing dyes can also be dissolved individually in the same or different solvents and the solutions can be mixed or added separately before being added to the emulsion. In the present invention, when the sensitizing dye is added to the silver monogenide photographic emulsion, the solvent for the dye may be, for example, methyl alcohol, alcohol, acetin, etc., which are compatible with water (a single solvent is preferable). In the present invention, when adding a sensitizing dye to a silver halide emulsion, the amount added is 1
0-' mole to 2.5XIQ-" mole, preferably 1
．． OX 10-'mol to 1. The sensitizing dye can be used in combination with other sensitizing dyes or supersensitizers. Prevents fogging during development processing,
Alternatively, for the purpose of stabilizing photographic performance, various compounds may be included to complete chemical ripening. For example, azoles such as penzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzimidazoles, aminotriazoles, benzotriazoles, nido c Nopenzotriazoles, mercaptetrazoles (especially 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines, mercaptotriazines,
For example, thioketo compounds such as oxazolinthione, as well as benzenethiosulfinic acid, benzenesulfinic acid, benzenesulfonic acid amide, hydroquinone derivatives,
Many compounds known as antifoggants or stabilizers can be added, such as aminophenol derivatives, gallic acid derivatives, ascorbic acid derivatives, etc. These compounds are preferably added during chemical ripening or before coating. Various hydrophilic colloids including gelatin are used as binders for the silver halide emulsion according to the present invention. Gelatin includes not only gelatin but also derivative gelatin, and derivative gelatin includes a reaction product of gelatin acid anhydride, a reaction product of gelatin and isocyanate, or a compound that harms gelatin and an active halogen atom. reaction products, etc. are included. Examples of the acid anhydride used in the reaction with gelatin include maleic anhydride, phthalic anhydride, benzoic anhydride, acetic anhydride, isatoic anhydride, and succinic anhydride, and examples of the isocyanate compound include, for example, phenyl anhydride. Examples include isocyanate, p-bromophenyl isocyanate, p-chlorophenylisocyanate, p-tolyl isocyanate, p-nitrophenyl isocyanate, naphthylisocyanate, and the like. Furthermore, examples of compounds having active halogen atoms include benzenesulfonyl chloride, p
-methoxybenzenesulfonyl chloride, p-phenoxybenzenesulfonyl chloride, p-bromobenzenesulfonyl chloride, p-toluenesulfonyl chloride, m-nitrobenzenesulfonyl chloride,
m-sulfobenzoyl dichloride, naphthalene-β-
Sulfonyl chloride, p-chlorobenzenesulfonyl chloride, 3-nitro-4-aminobenzenesulfonyl chloride, 2-carboxy-4-bromobenzenesulfonyl chloride, m-carboxybenzenesulfonyl chloride, 2-amino-5-methylhenzenesulfonyl Included are chlorite, phthalyl chloride, p-nitrobenozoyl chloride, hendiyl chloride, ethylchlorocarbonate-1., furoyl chloride, and the like. In addition to the above-mentioned derivative gelatin and ordinary photographic gelatin, hydrophilic colloids used to prepare silver halide emulsions include colloidal albumin, agar, gum arabic, dextran, alginic acid, such as acetyl-containing colloids, as necessary. Cellulose derivatives such as cellulose acetate hydrolyzed to 19-26%, polyacrylamide, imidized polyacrylamide, casein, vinyl alcohol, vinyl containing urethane carbonic acid groups or cyanoacedel groups such as pinylinanoacetate copolymer. Alcohol polymers, polyvinyl alcohol, polyvinylpyridine, hydrolyzed polyvinyl acetate, polymers obtained by polymerizing proteins or saturated acylated proteins with monomers having vinyl groups, polyvinylpyridine, polyvinylamine, polyaminoethyl methacrylate, polyethyleneimine, etc. are used. I can do it. Hardening of the emulsion is carried out according to conventional methods. The hardening agents used are common photographic film agents, such as aldehyde compounds such as formaldehyde, glyoxal, and glutaraldehyde, derivative compounds thereof such as acetals or sodium bisulfite adducts, and methanesulfonic acid esters. compounds, epoxy compounds,
Aziridine compounds, active halogen compounds, maleic imide compounds, active vinyl compounds, carbodiimide compounds, isoxazole compounds, N-medyrol compounds, isonanate compounds, or inorganic hardeners such as chromic bread, zirconium sulfate, etc. Membrane agents can be mentioned. The silver halide emulsion of the present invention contains a coating aid, an antistatic agent,
Various known surfactants may be included for various purposes such as improving shearing properties, emulsification and dispersion, preventing adhesion, and improving photographic properties (for example, development accelerator, contrast enhancement, and sensitization). That is, U.S. Patent 2
, 240.472, 2,831.766, 3,
15L4g No. 4, No. 3.210, No. 191, No. 3.29
No. 4,540, No. 3,507.660, British Patent No. 1,
No. 012,495, No. 1.022,878, No. 1.1
No. 79.290, No. 1.198,450, U.S. Patent No. 2
．． No. 739,891, No. 2,823,123, No. 1,
No. 179,290, same, No. 198.450, same 2,7
No. 39,891, No. 2,823.123, No. 3,06
No. 8,101, No. 3.415,649, No. 3,666
．． No. 478, No. 3,756,828, British Patent No. 1, 3
No. 97,218, No. 3゜113.816, No. 3,41
No. 1,413, No. 3,473.174, No. 3゜345
．． No. 974, No. 3.726.683, No. 3,843,
No. 368, Belgian Patent No. 731.126, British Patent No. 1
, No. 138.514, No. 1.159,825, No. 1,
No. 374,780, U.S. Pat. No. 2.271,623, U.S. Pat. No. 2,288,226, U.S. Pat.
, No. 235,919, No. 3.671,247, No. 3.
No. 772,021, No. 3.589,906, No. 3.6
No. 66.478, OLS No. 3.754,924, OLS No. 1,961,683, and Japanese Unexamined Patent Publication No. 1983-1
No. 17414, No. 50-59025, Special Publication No. 1974-3
No. 78, No. 40-379, and No. 43-■3822. For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl or alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkyl amines or amides) (classes, polyethylene oxide adducts of lincone)
, Grindol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, nonionic surfactants such as urethanes or ethers, triterpenoid saponins, Alkyl carboxylates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-anol-N-alkyl taurines, sulfosuccinates, sulfoalkylpolyoquine ethylene alkylphenyl ethers ,
Anisotropic active agents containing acidic groups such as carboquino groups, sulfo groups, phospho groups, sulfate ester groups, phosphoric ester groups such as polyoxyethylene alkyl phosphates, amino acids, aminoalkyl sulfonic acids , aminoalkyl sulfates or phosphoric acid esters, amphoteric surfactants such as alkyl hetaines, amine imides, amine oxides, alkyl amine salts, aliphatic or aromatic quaternary ammonium salts, pyridium, imidazolium, etc. Cationic surfactants such as heterocyclic quaternary ammonium salts and aliphatic or heterocyclic-containing sulfonium or sulfonium salts can be used. In addition to the above-mentioned surfactants, the silver halide emulsion of the present invention contains OLS 2.00 as a development accelerator.
No. 2,871, No. 2,445,611, No. 2,360
, No. 878, British Patent No. 1,352,196, etc., imidazoles, thioethers, selenoethers, etc. may be contained. In addition, in order to apply the silver halide emulsion of the present invention to a color photosensitive material, the red-sensitive silver halide emulsion of the present invention, the silver halide emulsion adjusted to have green sensitivity and blue sensitivity, cyan, magenta and The methods and materials used for color photosensitive materials may be used, such as incorporating a combination of yellow couplers, and the couplers are preferably non-diffusible 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 contain a colored coupler that has a color correction effect or a coupler that releases a development inhibitor during development (so-called DIR coupler). Additionally, the coupler may be such that the product of the coupling reaction is colorless. As the yellow coloring coupler, a known open-chain ketomethylene coupler can be used. Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous. A specific example of a yellow coupler that can be used is U.S. Patent No. 2.87.
No. 5,057, No. 3.265.506, No. 3.4H,
No. 194, No. 3,551.155, No. 3.582, 3
No. 22, No. 3,725,072, No. 3,891.44
No. 5, West German Patent No. 1,547,868, West German Application Publication (
OLS) No. 2,213,461, No. 2,219,917
No. 2.261゜361, No. 2,414,006, No. 2,263,875, etc. As the magenta coloring coupler, pyrazolone compounds, indacylon compounds, cyanoacetyl compounds, etc. can be used, and pyrazolone compounds are particularly advantageous. A specific example of a magenta color-forming coupler that can be used is disclosed in U.S. Pat.
, No. 600,788, No. 2,983゜608, No. 3.
No. 062,653, No. 3,127,269, No. 3,3
14゜476, 3.419.391, 3.51
No. 9,429, No. 3,558゜319, No. 3.582
No. 422, No. 3,615.506, No. 3,834゜9
No. 08, No. 3,891,445, West German Patent No. 1,810
, No. 484, West German Published Application (OLS) 2.468, 66
No. 5, No. 2,417.945, No. 2,418,959
No. 2,424,467, Japanese Patent Publication No. 40-6031, etc. As the cyan coloring coupler, phenol compounds, naphthol compounds, etc. can be used. A specific example is U.S. Patent No. 2,369,929, 2.4
No. 34,272, No. 2.474,293, No. 2.52
No. 1,908, No. 2,895.826, No. 3.834
, No. 892, No. 3,311.476, No. 3, 458,
No. 315, No. 3,476.563, No. 3.583,9
No. 71, No. 3.591゜383, No. 3,767.41
No. 1, West German Publication (OLS) No. 2,414°830,
It is described in No. 2,454,329 and Japanese Patent Application Laid-Open No. 48-59838. As a colored coupler, for example, U.S. Patent No. 3.476
．． No. 560, No. 2,521,908, No. 3. Q34.
No. 892, Special Publication No. 44-2016, No. 3g-2233
No. 5, No. 42-11304, No. 44-32461,
Patent application No. 49-98469, No. 50-118029,
The one described in OLS 2.418,959 can be used. As a DIR coupler, U.S. Pat. No. 3,227,554
No. 3,617,291, No. 3.701.783, No. 3.790.384, No. 3,632,345,
West German Publication (OLS) No. 2.414.006, 2.
Those described in No. 454,301, No. 2,454,329, British Patent No. 953.454, and Japanese Patent Application No. 146,570/1988 can be used. In addition to the DIR coupler, the light-sensitive material may also contain a compound that releases a development control agent upon development; for example, U.S. Pat.
The one described in No. 2, OLS No. 2.417.914 can be used. The pond, JP-A-55-8554
No. 9, No. 57-94752, No. 56-65134,
No. 56-135841, No. 54-130716, No. 5B-133734, No. 56-135841, U.S. Patent No. 4,310. [i18, British Patent 2.083,6
No. 40, Research Disclosure 18360 (1
979), 14850 (19H), 19033 (1
980), 19146 (1980), 20525 (
1931), 21728 (1982) can be used. Two or more of the above couplers can be contained in the same layer. Further, the same compound may be contained in two or more different layers. To introduce the coupler into the silver halide emulsion layer, known methods such as those described in US Pat. No. 2,322,027 can be used. For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.),
Phosphate esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid, esters (e.g. acetyl tributyl citrate), benzoate esters (e.g. octyl benzoate), alkyl amides (e.g. diethyl lauryl amide) ) etc., or boiling point of about 30°C to 1
506C organic solvents, such as low handling alkyl acetates such as ethyl acetate, butyl acetate, ethyl propionate, 2
After dissolving in butyl alcohol, methyl butyl ketone, β-ethquine ethyl acetate, methyl cellosolve acetate, etc., it is dispersed in a hydrophilic colloid. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be mixed and used. When the coupler has an acid group such as carboxylic acid or sulfonic acid, it is introduced into the hydrophilic colloid as an alkaline aqueous solution. These couplers are generally present in amounts ranging from 2 x 1o-3 moles to 5 x 10-' moles of silver per mole of silver in the silver halide emulsion layer.
moles, preferably l x 10-' moles to 5 x t
o-' moles are added. The photosensitive material produced using the present invention contains hydroquinone derivatives, aminophenol derivatives,
It may contain gallic acid derivatives, ascorbic acid derivatives, etc., and specific examples thereof include US Pat. No. 2,360,290,
2,336,327, 2,403,721, 2,418,613, 2,675,314, 2
, No. 701.197, No. 2,704,713, No. 2,
No. 128,659, No. 2,732,300, No. 2,7
35.765, JP-A No. 50-92988, JP-A No. 50-92988
No. 92989, No. 50-93928, No. 50-110
No. 337, Japanese Patent Publication No. 50-23813, etc. Effective antistatic agents include acetyl cellulose, styrene-fluoroalkyl sodium maleate copolymers, and alkali salts of reaction products of styrene-maleic anhydride copolymers and p-aminobenzenesulfonic acid. Examples of matting agents include polymethyl methacrylate, polystyrene, and alkali-soluble polymers. Furthermore, 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-sodium maleate copolymers, alkyl vinyl ether-maleic acid copolymers, and the like. Supports for photosensitive materials made using the silver halide emulsion prepared as described above include, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass paper, cellulose acetate, cellulose nitrate, polyvinyl Supports include acecool, polypropylene, polyester films such as polyethylene terephthalate, and polystyrene, and these supports are appropriately selected depending on the intended use of each photosensitive material. These supports are subjected to undercoat processing if necessary. After exposure, a light-sensitive material prepared using the silver halide emulsion of 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 hydroquine benzenes, aminophenols, and aminobenzenes, and other alkali metal salts such as sulfites, carbonates, and
May include bisulfites, bromides, and compounds. Further, when the light-sensitive material is for color use, it can be color-developed by a commonly used color development method. In the reversal method, the image is first developed with a black and white negative developer and then exposed to white light, or
Alternatively, the film is treated with a bath containing a fogging agent, and further color-developed with an alkaline phenomenon solution containing a color developing agent. There are no particular restrictions on the processing method, and any processing method can be applied; for example, a typical example is a bleach-fixing process after color development, followed by washing with water if necessary.
A method of performing stabilization treatment, or a method of performing bleaching and fixing separately after color development and further performing washing with water and stabilization treatment as necessary can be applied. The light-sensitive material according to the present invention has high sensitivity, low fog, and good storage stability, especially stability against heat, so that it can be applied to many uses. For example, it can be used for various purposes such as black and white general use, X-ray use, color use, infrared use, micro use, silver dye bleaching method, reversal use, and diffusion transfer method use. When applied to multilayer color light-sensitive materials, the present invention can be applied to various layer configurations well known in the art, including normal layer, reverse layer, and other layer configurations. [Examples] The present invention will be specifically explained below with reference to Examples. Example = 1 An emulsion containing 0.29 mol of regular octahedral silver bromide particles with an average grain size of 0.68 μm was dispersed in 1000+N4 distilled water (containing 30 mQ of 25% ammonia), and then 1-phenyl-5-mercaptotetrazole was added. Add 75 ml of 0.1% methanol solution to give a concentration of 0.47 mol/I2 at 50°C.
When 500 mg of silver nitrate aqueous solution and a mixed aqueous solution (containing 15 mol% potassium iodide) of necessary and sufficient potassium bromide and potassium iodide were used, pAgI was determined by the controlled double jet method.
Add over 30 minutes while controlling the temperature to 0.00 m, followed by 500 mf2 of a 0.47 mol/Q silver nitrate aqueous solution and a necessary and sufficient mixed aqueous solution of potassium bromide and potassium iodide (containing 2 mol% potassium iodide). was added in 20 minutes using a controlled double jet method while controlling the pA glo,o. Next, after desalting in a conventional manner, gelatin was added and redissolved. The emulsion thus produced was a core/shell emulsion with a high iodine phase inside, and as a result of electron microscopy observation, it was found that (11
0) Contained almost perfect rhombic dodecahedral grains consisting of crystal planes. This emulsion will be referred to as a type A emulsion. The emulsion was divided into seven parts, and sodium thiosulfate, dimethylselenourea, and chloroauric acid were added to each part, and ammonium tetrachloropalladate(n) was added to one of the emulsions and the other six emulsions as shown in Table 1. Chemical sensitization and spectral sensitization were performed under optimal conditions with varying amounts added. The Pd-free emulsion thus obtained was emulsion A, and the emulsions to which Pd was added were sequentially emulsions B, C, and D as shown in Table 1.
, E, F and G. The sensitizing dyes used for spectral sensitization are as follows. Each of the emulsions (A-G) obtained above contained 4-hydroxy-6-methyl-1,3,3a,7-titrazaindene, l-phenyl-5-mercaptotetrazole as a stabilizer, saponin as a coating aid, and hardener. 1.2 as a film agent
- Add appropriate amounts of bis(vinylsulfonyl)ethane and 3 g of polyvinylpyrrolidone, and then add the following color couplers, dodenrugalate, tricresyl phosphate, ethyl acetate, sodium triisopropylnaphthalene sulfonate, and gelatin dispersion, It was applied and dried to prepare samples (A-G). [Color coupler] Sensitometry of each of these samples was performed by the following method. The light source for exposure is a tungsten bulb (
An exposure of 1150 seconds was given through a filter and an optical wedge using a color temperature of 5400°K. Next, the following treatment was performed. Processing process (38℃) Processing time color development phenomenon
3 minutes 15 seconds bleach, 6 minutes 30 seconds water
Wash for 3 minutes and 15 seconds
Arrive: Wash for 6 minutes and 30 seconds
Stable bath for 3 minutes 15 seconds 1 minute 30
The composition of the treatment liquid used in each treatment step was as follows. [Color developer composition] "4-Amino-3-methyl-N-ethyl-1" 5. Log nitrilotriacetic acid trisodium salt (monohydrate) 1.20 g Sodium chloride
Add 0.14 g of water to make one volume, and adjust the pH to 10.20. [Bleach solution composition] Add ethylenediaminetetraacetic acid solution to 112 and adjust the pH to 6.0. [Fixer composition] Ammonium thiosulfate (70% aqueous solution) 175
．． 0g Anhydrous sodium sulfite 3.6
g 2.3 g of sodium metasulfite, add water to make +12, and adjust to I) 86.0. [Stabilizing liquid composition] Ropolmarin (37% aqueous solution) 5.
0mQ1″′. Da Guess (manufactured by Konishiroku Photo Industry Co., Ltd.)
7.5.e1 Add water to obtain IQ. The centometry results are shown in Table 1 below. Note that the sensitivity is expressed relative to the sensitivity of sample A as 100. Table 1 From the results in Table 1 above, by adding 10 to 100 parts of palladium salt to 1 part of gold salt in a stoichiometric ratio,
It is clear that low fog and high sensitivity can be achieved. Table 2 shows the results of examining the thermal stability of Samples A and D. From the above results in Table 2, it can be seen that the samples according to the present invention have improved storage stability at high temperatures, and in particular, an increase in fog can be suppressed. Example-2 Same grains as the type A emulsion of Example 1 (0.8 μm)
A non-core/Nel type emulsion was prepared with the same silver iodide content. That is, an emulsion containing 0.29 mol of regular octahedral silver bromide grains with an average grain size of 0.68 μm was mixed with 1000 m+ of distilled water! (2
containing 30ml of 5% ammonia) and then
Add 75 ml of 0.1% 1-phenyl-5-mercaptotetrazole methanol solution, and prepare at 50°C 1000 mg of a 0°47 mol/Q silver nitrate aqueous solution and a necessary and sufficient mixed aqueous solution of potassium bromide and potassium iodide (85 mol%).
(containing potassium iodide) was added over a period of 10 minutes while controlling pΔgio to 0 using a controlled double-noe method. Next, after desalting by a conventional method, gelatin was added and redissolved. As a result of electron microscopic observation, the silver iodobromide grains in this emulsion were found to be almost perfect rhombic dodecahedrons consisting of (110) crystal faces. This emulsion will be referred to as a type C emulsion. The surface emulsion was divided into two parts, and emulsion (2) was prepared corresponding to emulsion A in Example I and emulsion H1, and a type A emulsion (core/shell type) and a type C emulsion (non-core/shell type) were prepared. Table 3 shows the difference in Pd effect from the nonyl type). Note that the development processing conditions are also the same as in Example 1. Table 3 As is clear from Table 3, the effect of increasing sensitivity due to the addition of Pd salt is greater in the core-well type silver iodobromide emulsion than in the non-core/nonyl type. Example 3 An emulsion was prepared in exactly the same manner as the type Δ emulsion except that the same amount of methanol was used in place of the 1% methanol solution of 1-phenyl-5-mercaptotetrazole in Example I. As a result of electron microscopic observation, this emulsion was found to consist of almost perfect regular octahedral grains consisting of (111) crystal faces, and was core/nonyl type grains, and was classified as type C.
It is called emulsion. The emulsion was divided into two samples A and D of the type A emulsion.
Sample J was subjected to similar chemical sensitization and spectral sensitization to correspond to
and K were obtained and processed in the same manner, and the results are shown in Table 4. Furthermore, the test results regarding storage stability are shown in Table 5. Silver halide emulsions with dodecahedral crystals having (110) planes have a higher sensitivity effect due to the addition of Pd salt than silver halide emulsions with crystals in Table 4. Table 5 shows that Sample A according to the present invention has a greater effect of adding Pd salt than the octahedral crystal silver halide emulsion in terms of storage stability at high temperatures, and in particular, increases in fog are suppressed.

Claims (5)

[Claims] (1) In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support pair, at least one of the silver halide emulsion layers has a silver iodide content that differs between near the surface and inside. Silver iodobromide core/shell type silver halide grains having substantially (110) planes are treated with chalcogen sensitizers, gold sensitizers and noble metal compounds (Rh, Pd, Ir).
, a metal salt of Group VIII of the periodic table such as Pt)
A silver halide photographic material comprising a silver halide emulsion obtained by chemical sensitization in the presence of seeds. (2) The above noble metal compound has the following general formula (1) or (
The silver halide photographic light-sensitive material according to claim 1, which is a compound represented by 2). General formula (1) R_2MX_4 General formula (2) R_3M'
X_6 [wherein, R represents a hydrogen atom, an ammonium group, or an alkali metal atom, M represents Pt or Pd, and M' represents I
Represents r or Rh. Moreover, X represents a halogen atom. ] (3) The amount of the compound represented by the general formula in the preceding paragraph is 10:1 to 100:1 in stoichiometric ratio (mole ratio) to the gold sensitizer.
The silver halide photographic light-sensitive material according to claims 1 and 2, characterized in that the silver halide photographic light-sensitive material falls within the following range. (4) The silver halide photographic photosensitive material according to claim 1, 2 or 3, wherein the chemical sensitization is carried out in the presence of at least one of the Pd compound and the Ir compound. material. (5) The silver halide photographic material according to any one of claims 1 to 4, wherein the silver halide photographic material is chemically sensitized in the presence of a Pd compound among the noble metal compounds.