JP3001346B2 - Silver halide emulsion and silver halide photographic material using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material, and more particularly to a silver halide emulsion having excellent photographic sensitivity and a photographic material using the emulsion.

[0002]

2. Description of the Related Art Many silver halide emulsions used in the production of silver halide photographic light-sensitive materials contain silver halide compound crystals of a type having two crystal planes. These are crystals formed by {100} planes and / or {111} planes.

A. MIGNOT, E .; FRANCOIS
AND M. CATINAT, "CRISTAUX
DE RBOMURE D'ARGENT PLAT
S, LIMITES PAR DES FACES (1
00) ET NON MACLES ", Journal
of Crystal Growth 123 (19
74) According to the report of 207-213, tabular silver bromide crystals formed of {100} planes having a square or rectangular main plane are observed.

According to the disclosure of US Pat. No. 4,063,951, tabular grains formed by {100} crystal faces are formed from monodisperse seed grains, and when ripened in the presence of ammonia, the tabular grains are averaged. Aspect ratio 1.5
7 is formed. U.S. Pat. No. 4,386,156 discloses a tabular silver bromide emulsion formed to have an average aspect ratio of 8 or more by ripening seed grains in the absence of a non-halide silver ion complexing agent. Is shown. A method for producing tabular grains having a high silver chloride content is disclosed in EP 534,395 A1.

As described above, there are reports of emulsions occupied by tabular silver halide grains having a {100} crystal plane as a main plane. However, since all of these emulsions are produced only by nucleation and ripening, they have been reported. There are problems that the yield of silver emulsion is low and that the grain size cannot be freely controlled.
Further, when these are used as a silver halide photographic light-sensitive material, further improvement is required particularly from the viewpoint of photographic sensitivity.

[0006]

SUMMARY OF THE INVENTION The present invention relates to {100}
A silver halide emulsion having excellent color sensitization sensitivity by providing a method for producing a tabular grain emulsion having a principal plane as a main surface in a high yield, and containing iodine as a halogen composition in the silver halide; An object of the present invention is to provide a photographic light-sensitive material using an emulsion.

[0007]

Means for Solving the Problems The object of the present invention is to provide:
(1) Two parallel main planes are {100} planes, the aspect ratio is 2 or more, the average silver chloride content of the grains is 60 mol% or more, and the silver iodide content of the grain surfaces is 1 or more. A silver halide emulsion characterized in that tabular silver halide grains of at least mol% occupy at least 50% of the total projected area of the silver halide grains. (2) a silver halide photographic material, wherein at least one silver halide emulsion layer provided on a support contains the silver halide emulsion described in (1) above; The silver halide photographic material according to the above (2), wherein the silver iodide content on the surface of the silver halide grains is 2.5 mol% or more.
(4) The silver halide photographic material as described in (2) above, wherein the tabular silver halide grains are sensitized with gold and sulfur, and (5) the tabular silver halide grains are a cyanine dye. The silver halide photographic material as described in (2) above, which is spectrally sensitized by
(6) The silver halide photographic material as described in (2) above, wherein the tabular silver halide grains are sensitized with gold and sulfur in the presence of a cyanine dye.

The silver halide emulsion of the present invention will be described below.

The emulsion of the present invention is produced through at least nucleation and ripening steps. First, the nucleation process will be described in order. 1) Nucleation Step An AgNO ₃ solution and a halide salt (hereinafter referred to as X ⁻ salt) solution are added to a dispersion medium solution containing at least a dispersion medium and water by stirring at the same time to form nuclei. The Cl ⁻ concentration in the dispersion medium solution at the time of nucleation is preferably 10 ^−1.5 mol / l or less, and the Ag ⁺ concentration is preferably 10 ⁻² mol / l or less. The pH is preferably 2 or more, more preferably 5 to 10. The gelatin concentration is preferably from 0.1 to 3% by weight, more preferably from 0.2 to 2% by weight.

The temperature at the time of nucleation is not limited.
0 ° C. or higher is preferable, and 20 to 70 ° C. is preferable. After nucleation, physical ripening is performed to eliminate non-tabular grains and grow the tabular grains. The addition rate of Ag ⁺ salt is preferably 0.5 to 20 g / min per liter of the container solution, and 1 to 15 g / min.
g / min is more preferred. Although the pH of the container solution is not particularly limited, it is usually pH 1 to 11, preferably pH 3 to 10. The most preferable pH value can be selected and used according to the combination of the excess Ag ⁺ concentration, the temperature, and the like.

The I ^- content of the AgX nucleus formed at the time of nucleation is preferably 10 mol% or less, more preferably 5 mol% or less. 2) Ripening process It is not possible to make only tabular grain nuclei during nucleation. Therefore, tabular grains are grown by Ostwald ripening in the next ripening step, and other grains are extinguished. The aging temperature is 40 ° C or higher, preferably 50 to 90 ° C, more preferably 55 to 80 ° C.

The excess Cl ^- concentration during aging is 10 ^-1.2 to 10
^-4 mol / l is preferred, and 10 ^-1.5 to 10 ^-3 mol / l
Liters are more preferred.

In the present invention, the ripening is substantially carried out using NH.
₃ does not coexist. Here, the expression "substantially no coexistence of NH _3" means that the NH ₃ concentration is lower than 0.1 mol / l, preferably 0.05 mol / l or less, more preferably 10 ^-2 mol / l or less. It is preferable that an AgX solvent other than NH ₃ is not substantially allowed to coexist. Here, “substantially” means that the concentration of the AgX solvent Z ₀ is preferably Z _0.
0 ≦ 0.5 mol / liter, more preferably Z ₀ <0.
1 mol / liter, more preferably Z ₀ <0.02 mol / liter. This is because the fog density increases. During ripening, the silver salt solution and the X ^- salt solution can be added at a low rate while maintaining various conditions. Here, the low rate refers to preferably 30% or less, more preferably 20% or less of the critical addition rate.

At the end of ripening, the AgX emulsion of the present invention can be prepared, but usually, a growth process is provided for the following requirements. That is, 1) to obtain emulsion particles of a desired particle size, 2) to increase the molar yield of AgX, and 3) AgX layers having different halogen compositions are laminated with the particles as core particles, and core / shell type particles are formed. To form, or to form a multi-structure particle composed of a core and two or more shell layers. When the emulsion of the present invention is obtained at the end of the ripening, it is necessary to ripen the emulsion until the total projected area of the tabular grains falls within the above range. Next, when a growth process is provided, it is preferable that the total projected area of the tabular grains falls within the above range at the end of ripening.

The pH during aging is from 1 to 12, preferably from 2 to
8, more preferably 2 to 6. 3) Growth process The excess ion concentration of Ag ⁺ and Cl ⁻ was 10 ^−2.3 mol /
When crystals are grown near the equivalent point of less than 1 liter, preferably less than 10 ^-2.6 mol / l, the grains grow preferentially in the edge direction. The growth conditions may be selected so that the finally obtained AgX emulsion satisfies the above requirements.

Examples of the method of adding the solute during the growth include a method of adding a silver salt solution and an X ^- salt solution simultaneously, a method of adding a previously formed AgX fine grain emulsion, and a combination of both. Of these, the method is more preferred. This is because the supersaturation concentration during grain growth is uniformly and precisely controlled by the solubility of the coexisting fine particles. As in the case of the parallel twin plane type tabular grains, the supersaturation concentration must be precisely controlled in order to control (line growth rate of main plane / line growth rate of edge portion) = x of tabular grains. And meet the objectives of the present invention. Normally, as the supersaturated concentration increases, x
Increase and become monodisperse. On the other hand, when the supersaturation concentration is reduced, x decreases, and polydispersion occurs. Thus, the supersaturation concentration is not too high and not too low and needs to be optimally and uniformly adjusted, but the method of adding fine particles makes this possible.

The diameter of the fine particles is preferably 0.15 μm or less, more preferably 0.1 μm or less, and further preferably 0.06 μm or less. The fine grain emulsion can be added continuously or intermittently. The fine grain emulsion can be continuously prepared by supplying the AgNO ₃ solution and the X ⁻ salt solution by a mixer provided near the reaction vessel, and can be immediately added to the reaction vessel immediately or in another vessel in advance. And then added continuously or intermittently. The fine grain emulsion can be added in a liquid form or as a dry powder.
The fine particles preferably do not substantially contain multiple twin particles. Here, the multiple twin particles refer to particles having two or more twin planes per particle. Substantially not included
A multiple twin particle number ratio of 5% or less, preferably 1% or less;
More preferably, it refers to 0.1% or less. Further, it is preferable that substantially no single twin particles are contained. Further, it is preferable that the composition does not substantially include a screw dislocation. Here, "substantially not contained" complies with the above-mentioned ratio regulation.

The halogen composition of the fine particles is AgCl, AgB
r, AgBrI (I ^- content is preferably 20 mol% or less, more preferably 10 mol% or less, and still more preferably 5 mol% or less) and a mixed crystal of two or more thereof.

The solution conditions at the time of grain growth are the same as those at the time of ripening. Both are steps for growing tabular grains by Ostwald ripening and eliminating other fine particles, and are mechanically the same. For details of the general method of adding the fine grain emulsion, see Japanese Patent Application No. 2-1263 / 1990.
5, 4-77261 and JP-A-1-183417. In order to form fine particles substantially free of twin planes, excess X ^- concentration or excess A
The g ⁺ concentration is preferably below 10 ⁻² mol / l,
It may be formed by adding the g ⁺ salt solution and the X ^- salt solution by a simultaneous mixing addition method.

The temperature for forming fine particles is preferably 50 ° C. or less,
5-40 degreeC is more preferable, and 10-30 degreeC is more preferable. The dispersion medium preferably has a molecular weight of 2,000 to 6 × 10
⁴ , more preferably 5000 to ⁴ × 10 ⁴ low molecular weight gelatin is preferably 30% by weight or more, more preferably 6% by weight or more.
Gelatin occupying 0% by weight or more, more preferably 80% by weight or more is preferred. The concentration of the dispersion medium is preferably 0.2% by weight or more, more preferably 0.5 to 5% by weight.

[0021] Although not substantially coexist NH ₃ during aging in the present invention, it is preferable that the nucleation process does not substantially coexist NH _3. Here, “substantially” complies with the above-mentioned rules. It is preferable not to allow NH ₃ to coexist during the growth.
Here, “substantially” means that the NH ₃ concentration Z ₁ is Z ₁ ≦ 0.5 mol / l, more preferably Z ₁ <0.1 mol / l, and still more preferably Z ₁ <0.02 mol / l. Means that. It is preferable that substantially no AgX solvent other than NH ₃ coexist in the nucleation and growth processes.
Here, “substantially” is the same as the above Z ₁ concentration regulation. N
Examples of the AgX solvent other than H ₃ include antifoggants such as thioethers, thioureas, thiocyanates, organic amine compounds, and tetrazaindene compounds. Preferably, thioethers, thioureas, Thiocyanate.

Since the tabular grains of the present invention are prepared under conditions in which fogging nuclei are likely to occur, the resulting emulsion may have a high fog density. Normally, the fog increases as the temperature increases,
The higher the H, the higher the Ag ⁺ concentration, the higher. The fog generated in the grain formation process can be removed by performing a process of oxidizing silver nuclei after each step or after completion of all steps of grain formation. The oxidation potential of the system may be higher than the oxidation potential of silver nuclei. The details can be referred to the description in Japanese Patent Application No. 4-145031.

In order to reduce the fogging concentration, a thiosulfonic acid compound may be added during or after the formation of the particles. These are disclosed in JP-A-4-156.
448, European Patents 0435355 A1 and 043527
0A1 and 0348934A2 can be referred to.

During the grain formation, dislocation lines can be introduced into the grains by a halogen composition gap method, a halogen conversion method, an epitaxial growth method or a combination thereof. Pressure fogging characteristics, reciprocity characteristics, and color sensitization characteristics are further improved and are preferable. Regarding this, JP-A-63-2
20238, 64-26839, JP-A-2-1276
35, 3-189644, 3-175440, 2
−123346, European Patent 0460656A1 Journal
of Imaging Science, 32, 160-177 (19
88) can be referred to.

The obtained particles may be used as host particles to form epitaxial particles for use. Further, particles having dislocation lines therein may be formed using the particles as a core.
Alternatively, the particles may be used as a substrate, and AgX layers having a different halogen composition from the substrate may be laminated to produce various known particles having various particle structures. Regarding these, the description in the following literature can be referred to.

Further, a shallow inner latent emulsion may be formed by using the tabular grains as a core. Also, core / shell type particles can be formed. This is described in
No. 133542, No. 63-151618, U.S. Pat. Nos. 3,206,313, 3,317,322, 3,761,276, 4,269,927, and 3,367,778. Can be referred to.

As described above, the most important parameter for obtaining silver halide grains having a high aspect ratio is pAg during ripening and growth, and the aspect ratio of tabular grains in the present invention is 2 or more. 100 or less. The aspect ratio is preferably 3 or more and 50 or less, and 4
It is more preferable that the number be 30 or more and 30 or less. The aspect ratio is preferably in the above range mainly due to the balance between sensitivity and pressure.

As used herein, the term "aspect ratio" refers to the ratio of the thickness between major planes to the average edge length forming the major planes of the grains, and the "major plane" substantially forms cuboid emulsion grains. Of the crystal surface, the plane is defined as a set of parallel surfaces having the largest area, and the fact that the principal plane is a {100} plane can be determined by an electron diffraction method or an X-ray diffraction method. A substantially cuboid emulsion grain has a principal plane of $ 10.
Although it is formed from the {0} plane, it means that it may have 1 to 8 {111} crystal planes. That is, one to eight of the eight corners of the rectangular parallelepiped may have a rounded shape. The “average edge length” is defined as the length of one side of a square having an area equal to the projected area of each grain as viewed in a micrograph of the emulsion grain sample.

The present invention is based on the invention that iodine is contained in the surface of tabular grains having a {100} plane as a main plane formed through a nucleation step, an ripening step, and a growing step.
The average silver chloride content in the tabular grains present in the emulsion is not less than 60 mol% and less than 100 mol%, preferably not less than 70 mol% and not more than 99.99 mol%, 80 mol% or more and 99.95 mol%
It is more preferred that: The silver halide grains of the present invention may contain bromine ions, but are preferably substantially silver chloroiodide grains. Here, “substantially” means that bromide ions are contained in only 1 mol% or less.

In the present invention, the silver iodide content on the surface of the silver halide grains can be detected by various surface elemental analysis means. It is effective to use a method such as XPS, Auger electron spectroscopy, and ISS. XPS (X-ray Photoelectron) is the simplest and most accurate means.
Spectroscopy).

XPS (X-ray Photoelec)
It is said that the depth analyzed by a Tron Spectroscopy (Surface Spectroscopy) surface analysis method is about 10A.

For the principle of the XPS method used for analyzing the iodine content near the surface of silver halide grains, refer to “Electron Spectroscopy” by Junichi Aihara et al. (Kyoritsu Library 16, Kyoritsu Shuppan, 1978). Can be

The standard XPS measurement method uses Mgkα as excited X-rays, and the iodine (I) and silver (Ag) photoelectrons (usually I -3d5 _{/ 2} , Ag-3d5 _{/ 2} ).

In order to determine the iodine content, iodine (I) and silver (A) were obtained using several types of standard samples having known iodine contents.
The calibration curve of the intensity ratio (intensity (I) / intensity (Ag)) of the photoelectrons in g) can be prepared and determined from this calibration curve.
In a silver halide emulsion, XPS must be measured after gelatin adsorbed on the surface of silver halide grains is decomposed and removed by a protease or the like.

The silver iodide content in the vicinity of the grain surface of the tabular grains in the present invention can be determined by the XPS surface analysis method described above, and the value is preferably from 1 mol% to 10 mol%. , 2.5 mol% or more and 7 mol% or less.

The tabular grains in the present invention occupy 50% or more, preferably 60% or more, and more preferably 70% or more of the total projected area of the silver halide grains. In each case, the upper limit is 100%.

The light-sensitive material of the present invention may be provided with at least one of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer of a silver halide emulsion layer on a support. There is no particular limitation on the number and order of the silver halide emulsion layer and the non-photosensitive layer. A typical example is a silver halide photographic light-sensitive material having at least one light-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. Wherein the photosensitive layer is blue light, green light,
And a unit light-sensitive layer having color sensitivity to any of red light, and in a multilayer silver halide color photographic light-sensitive material, the arrangement of the unit light-sensitive layers is generally such that the red-sensitive layer, green The color-sensitive layer and the blue-sensitive layer are provided in this order. However, depending on the purpose, the order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched between layers of the same color sensitivity.

Non-light-sensitive layers such as various intermediate layers may be provided between the silver halide light-sensitive layers and as the uppermost layer and the lowermost layer.

The intermediate layer has a structure described in JP-A-61-43748.
No. 59-113438, No. 59-113440
Couplers, DIR compounds and the like described in JP-A Nos. 61-20037 and 61-20038 may be contained, and a color mixture inhibitor may be contained as usually used.

As described in West German Patent No. 1,121,470 or British Patent No. 923,045, a plurality of silver halide emulsion layers constituting each unit photosensitive layer may be composed of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer. A two-layer constitution of an emulsion layer can be preferably used. Usually, it is preferable to arrange them so that the light sensitivity decreases sequentially toward the support, and a non-photosensitive layer may be provided between the respective halogen emulsion layers. Also,
JP-A-57-112751, 62-200350
As described in JP-A Nos. 62-206541 and 62-206543, a low-speed emulsion layer may be provided on the side farther from the support and a high-speed emulsion layer may be provided on the side closer to the support.

As a specific example, from the side farthest from the support,
Low-sensitivity blue-sensitive layer (BL) / High-sensitivity blue-sensitive layer (BH)
/ High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (G
L) / high-sensitivity red-sensitive layer (RH) / low-sensitivity red-sensitive layer (RL), or BH / BL / GL / GH / RH /
RL order or BH / BL / GH / GL / RL / RH
And so on.

As described in JP-B-55-34932, the layers may be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the farthest side from the support. JP-A-56-25738 and JP-A-62-6393.
As described in the specification of JP-A No. 6, the blue light-sensitive layer / GL / RL / GH / RH may be arranged in this order from the farthest side from the support.

Further, as described in JP-B-49-15495, the upper layer is the silver halide emulsion layer having the highest sensitivity, the middle layer is the silver halide emulsion layer having a lower sensitivity, and the lower layer is the middle layer. Further, an arrangement is also possible in which a silver halide emulsion layer having a lower sensitivity is further disposed, and an arrangement is formed of three layers having different sensitivities in which the sensitivities are successively decreased toward the support. Even in the case of three layers having different sensitivities, as described in JP-A-59-202264, a medium-sensitivity emulsion from the side farther from the support in the same color-sensitive layer. Layers / high-speed emulsion layers / low-speed emulsion layers.

In addition, a high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or a low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer may be arranged in this order.

In the case of four or more layers, the arrangement may be changed as described above.

As described above, various layer configurations and arrangements can be selected according to the purpose of each photosensitive material.

In the photographic light-sensitive material of the present invention, at least one silver halide emulsion layer provided on a support contains 30% or more, preferably 50% or more, more preferably 30% or more of the silver halide emulsion of the present invention. This is a silver halide photographic material containing 70% or more.

The silver halide other than the silver halide of the present invention contained in the photographic emulsion layer of the photographic light-sensitive material of the present invention is about 3%.
Silver iodobromide, silver iodochloride, or silver iodochlorobromide containing 0 mol% or less of silver iodide is preferred. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% of silver iodide. However, it is preferable that the silver bromide content in the whole photographic material is low, and that the silver iodide content is also low.

The silver halide grains in the photographic emulsion other than the silver halide of the present invention have regular crystals such as cubic, octahedral and tetradecahedral, and irregular grains such as spherical and plate-like. It may be a material having a suitable crystal form, a material having a crystal defect such as a twin plane, or a complex form thereof.

The silver halide other than the silver halide of the present invention may be fine grains having a grain size of about 0.2 μm or less or large grains having a projected area diameter of about 10 μm. A dispersion emulsion may be used.

The silver halide photographic emulsion usable in the present invention is, for example, Research Disclosure (RD) N
o. 17643 (December 1978), pp. 22-23,
"I. Emulsion preparat
ion and types) ", and No. 18 of the same.
716 (November 1979), p. 648, ibid. 30
7105 (November 1989), pp. 863-865, and "Physics and Chemistry of Photography" by Grafkid, published by Paul Montell (P. Glafkides, Chemieet).
Physique Photographique, P
aul Montel, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (GF Duff).
in, Photographic Emulsion
Chemistry (Focal Press, 196
6)), "Manufacture and Coating of Photographic Emulsions", by Zerikman et al., Published by Focal Press (VL Zelikmanet).
al. , Making and Coating Ph
autographic Emulsion, Focal
Press, 1964) and the like.

US Pat. Nos. 3,574,628;
655,394 and British Patent 1,413,748.
Monodisperse emulsions described in Nos. 1 and 2 are also preferred.

Tabular grains having an aspect ratio of about 3 or more can also be used in the present invention. Tabular grains are described by Gatov, Photographic Science and Engineering (Gutoff, Photograph).
ic Science and Engineerine
g), Vol. 14, pp. 248-257 (1970));
U.S. Pat. Nos. 4,434,226 and 4,414,31
No. 0, 4,433,048, 4,439,520
And British Patent No. 2,112,157.

The crystal structure may be uniform, the inside and outside may have different halogen compositions, or may have a layered structure. Also, silver halides having different compositions may be joined by epitaxial junction. May be
Further, it may be bonded to a compound other than silver halide such as, for example, silver rhodan or lead oxide. Also, a mixture of particles of various crystal forms may be used.

The above emulsion may be either a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which the latent image is formed inside the grains, or a type having a latent image on both the surface and the inside. It is preferably a type emulsion. Among the internal latent image type emulsions, core / shell type internal latent image type emulsions described in JP-A-63-264740 may be used. A method for preparing this core / shell type internal latent image type emulsion is described in JP-A-59-133.
No. 542. The thickness of the shell of this emulsion varies depending on the development process and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

The silver halide emulsion used in the present invention is usually subjected to physical ripening, chemical ripening and spectral sensitization.

A method of adding a chalcogen compound during preparation of an emulsion as described in US Pat. No. 3,772,031 is sometimes useful. In addition to S, Se, and Te, cyanide, thiocyanate, selenocyanic acid, carbonate, phosphate, and acetate may be present.

The silver halide grains used in the present invention are prepared by subjecting at least one of sulfur sensitization, selenium sensitization, gold sensitization, palladium sensitization or other noble metal sensitization and reduction sensitization to a silver halide emulsion production process. Can be applied in any process.
It is preferable to combine two or more sensitization methods. Various types of emulsions can be prepared depending on the step of chemical sensitization. There are a type in which a chemical sensitizing nucleus is embedded in the grain, a type in which the chemical sensitizing nucleus is embedded in a position shallow from the grain surface, and a type in which a chemical sensitizing nucleus is formed on the surface. In the emulsion of the present invention, the location of the chemical sensitization nucleus can be selected according to the purpose. Generally, the case where at least one type of chemical sensitization nucleus is formed near the surface is preferred.

One of the chemical sensitizations which can be preferably carried out in the present invention is a chalcogen sensitization and a noble metal sensitization alone or in combination, which is described in TH James, The Photographic Process, No. 4. Edition, published by Macmillan, 1
977, (TH James, The Theor)
y of the PhotographicProc
ess, 4th ed, Macmilllan, 197
7) It can be carried out using active gelatin as described on pages 67-76, and can also be performed by Research Disclosure 120, April 1974, 12008; Research Disclosure 34, June 1975, 1
3452, U.S. Pat. Nos. 2,642,361 and 3,2
97,446, 3,772,031, 3,85
7,711, 3,901,714, 4,26
6,018, and 3,904,415, and British Patent 1,315,755.
It can be sulfur, selenium, tellurium, gold, platinum, palladium, iridium or a combination of a plurality of these sensitizers at Ag 5-10, pH 5-8 and temperature 30-80 ° C. In the noble metal sensitization, noble metal salts such as gold, platinum, palladium, and iridium can be used, and among them, gold sensitization, palladium sensitization, and a combination of both are preferable. In the case of gold sensitization, known compounds such as chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, and gold selenide can be used. The palladium compound means a divalent palladium salt or a tetravalent salt. Preferred palladium compounds are represented by R ₂ PdX ₆ or R ₂ PdX ₄ . Where R is a hydrogen atom,
Represents an alkali metal atom or an ammonium group. X represents a halogen atom, and represents a chlorine, bromine or iodine atom.

Specifically, K ₂ PdCl ₄ , (NH ₄ )
₂ PdCl ₆ , Na ₂ PdCl ₄ , (NH ₄ ) ₂ PdC
l ₄ , Li ₂ PdCl ₄ , Na ₂ PdCl ₆ or K ₂
PdBr ₄ is preferred. The gold compound and the palladium compound are preferably used in combination with a thiocyanate or a selenocyanate.

As sulfur sensitizers, hypo, thiourea compounds, rhodanine compounds and US Pat. No. 3,857,
Nos. 711, 4,266,018 and 4,05
Sulfur-containing compounds described in US Pat. No. 4,457 can be used. Chemical sensitization can also be performed in the presence of a so-called chemical sensitization aid. Useful chemical sensitization aids include compounds known to suppress fog and increase sensitivity during chemical sensitization, such as azaindene, azapyridazine and azapyrimidine. Examples of chemical sensitization aid modifiers are described in U.S. Pat.
Nos. 411,914 and 3,554,757;
No. 8-126526 and the above-mentioned "Photographic Emulsion Chemistry" by Duffin, pp. 138-143.

The emulsion of the present invention is preferably used in combination with gold sensitization and sulfur sensitization. The preferred amounts of the gold sensitizer and the sulfur sensitizer are each 1 × 1 per mol of silver halide.
0 ^-4 to 1 × 10 ^-7 mol, more preferably 1 × 10 ^-7 mol.
It is 10 ^{-5 to} 5 × 10 ^-7 mol.

Selenium sensitization is a preferred sensitization method for the emulsion of the present invention. In the selenium sensitization, a known unstable selenium compound is used, and specifically, colloidal metal selenium, selenoureas (eg, N, N-dimethylselenourea, N, N-diethylselenourea, etc.), selenoketone And selenium compounds such as selenoamides can be used. It may be preferable to use selenium sensitization in combination with sulfur sensitization and / or noble metal sensitization.

During the grain formation of the silver halide emulsion of the present invention,
It is preferable to perform reduction sensitization after grain formation and before or during chemical sensitization, or after chemical sensitization.

Here, reduction sensitization refers to a method in which a reduction sensitizer is added to a silver halide emulsion, and a pAg 1 called silver ripening.
7, a method of growing or ripening in a low pAg atmosphere, or a method of growing or ripening in a high pH atmosphere of pH 8-11 called high pH ripening. Also, two or more methods can be used in combination.

The method of adding a reduction sensitizer is a preferable method since the level of reduction sensitization can be finely adjusted.

Known reduction sensitizers include stannous salts, ascorbic acid and its derivatives, amines and polyamines, hydrazine derivatives, formamidinesulfinic acid, silane compounds and borane compounds. For the reduction sensitization of the present invention, these known reduction sensitizers can be selected and used, and two or more compounds can be used in combination. Stannous chloride, thiourea dioxide, dimethylamine borane, ascorbic acid and derivatives thereof are preferred compounds as reduction sensitizers. Since the addition amount of the reduction sensitizer depends on the emulsion production conditions, it is necessary to select the addition amount, but an appropriate range is from 10 ^-7 to 10 ^-3 mol per mol of silver halide.

The reduction sensitizer is dissolved in water or a solvent such as alcohols, glycols, ketones, esters, and amides and added during grain growth. Although it may be added to the reaction vessel in advance, it is preferable to add it at an appropriate time during grain growth. Alternatively, a reduction sensitizer may be added in advance to the water solubility of a water-soluble silver salt or a water-soluble alkali halide, and silver halide grains may be precipitated using these aqueous solutions. It is also a preferred method to add the solution of the reduction sensitizer in several portions as the grains grow, or to add the solution continuously for a long time.

It is preferable to use an oxidizing agent for silver during the production process of the emulsion of the present invention. The oxidizing agent for silver is
A compound that acts on metallic silver to convert it into silver ions. In particular, a compound that converts extremely fine silver grains by-produced during the formation process of silver halide grains and the chemical sensitization process into silver ions is effective. The silver ions generated here may form a silver salt which is hardly soluble in water such as silver halide, silver sulfide or silver selenide, or a silver salt which is easily soluble in water such as silver nitrate. Is also good. The oxidizing agent for silver may be inorganic or organic. Examples of the inorganic oxidizing agent include ozone, hydrogen peroxide and adducts thereof (eg, NaBO ₂ .H ₂ O ₂ .3H ₂ O, 2NaC
_{O 3 · 3H 2 O 2,} Na 4 P 2 O 7 · 2H 2 O 2, 2N
a ₂ SO ₄ .H ₂ O ₂ .2H ₂ O), peroxy acid salts (eg, K ₂ S ₂ O ₈ , K ₂ C ₂ O ₆ , K ₂ P)
₂ O ₈ ), peroxy complex compounds (for example, K ₂ [Ti
_{(O 2) C 2 O 4} ] · 3H 2 O, 4K 2 SO 4 · Ti
(O ₂ ) OH · SO ₄ · 2H ₂ O, Na ₃ [VO
(O ₂ ) (C ₂ H ₄ ) ₂ ] · 6H ₂ O), permanganate (eg, KMnO ₄ ), chromate (eg, K ₂
Oxyacids such as Cr ₂ O ₇ ), halogen elements such as iodine and bromine, perhalates (eg, potassium periodate),
High-valent metal salts (eg, potassium hexacyanoferrate) and thiosulfonates.

Examples of the organic oxidizing agent include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds which release active halogen (eg, N-bromosuccinimide, chloramine T). Preferred oxidants of the present invention, for example, chloramine B), are ozone, hydrogen peroxide and its adducts, halogen elements, inorganic oxidants of thiosulfonates and organic oxidants of quinones. It is a preferred embodiment to use the above-described reduction sensitization and an oxidizing agent for silver in combination. The method can be selected from a method of performing reduction sensitization after using an oxidizing agent, a method reverse thereto, or a method of coexisting the two simultaneously. These methods can be selectively used in both the grain formation step and the chemical sensitization step.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the photographic material, or stabilizing photographic performance. . That is, thiazoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (especially 1-phenyl-5-mercaptotetrazole) and the like; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadrinethione; azaindenes such as tria Zaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,
Many compounds known as antifoggants or stabilizers, such as 3,3a, 7) tetraazaindenes, pentaazaindenes and the like can be added. For example, U.S. Patent Nos. 3,954,474 and 3,982,9
No. 47 and JP-B No. 52-28660 can be used. One of the preferred compounds is disclosed in
There is a compound described in JP-A-3-212932. Antifoggants and stabilizers are used at various times before, during and after particle formation, during the water washing step, during dispersion after water washing, before chemical sensitization, during chemical sensitization, after chemical sensitization, and before coating. It can be added according to the purpose. In addition to exhibiting the original antifogging and stabilizing effects by adding during emulsion preparation, control the crystal habit of the grains, reduce the grain size, reduce the solubility of the grains, control the chemical sensitization, It can be used for various purposes such as controlling the arrangement of dyes.

The photographic emulsion used in the present invention is preferably spectrally sensitized by a methine dye or the like to exhibit the effects of the present invention. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei usually used for cyanine dyes as basic heterocyclic nuclei can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiozoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, and the like; A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of
That is, an indolenine nucleus, a benzindolenin nucleus, an indole nucleus, a benzoxadol nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, and a quinoline nucleus can be applied. These nuclei may have a substituent on a carbon atom.

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

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for supersensitization. Representative examples are U.S. Pat. Nos. 2,688,545 and 2,972.
7,229, 3,397,060, 3,52
2,052, 3,527,641, 3,61
7,293, 3,628,964 and 3,66
6,480, 3,672,898, 3,67
9,428, 3,703,377, 3,76
9,301, 3,814,609, 3,83
Nos. 7,862, 4,026,707, British Patent Nos. 1,344,281, 1,507,803, JP-B-43-4936, JP-B-53-12,375, JP-A-52 Nos. -110,618 and 52-109,925.

In addition to the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization.

The sensitizing dye may be added to the emulsion at any stage in the preparation of the emulsion which has hitherto been known to be useful. Most commonly, it is performed after completion of chemical sensitization but before coating, but US Pat.
As described in JP-A Nos. 8,969 and 4,225,666, spectral sensitization can be carried out simultaneously with chemical sensitization by simultaneous addition with a chemical sensitizer.
It can be carried out prior to chemical sensitization as described in US Pat. No. 3,928, or can be added prior to completion of silver halide grain precipitation to start spectral sensitization. Furthermore, these compounds may be added separately as taught in U.S. Pat. No. 4,225,666, i.e., some of these compounds may be added prior to chemical sensitization and the remainder chemically sensitized. It is also possible to add the silver halide grains after the silver halide grains have been formed, and may be added at any time during the formation of silver halide grains, including the method disclosed in U.S. Pat. No. 4,183,756.

The silver halide emulsion of the present invention is preferably spectrally sensitized with a cyanine dye, and the sensitizing dye is preferably added to the emulsion at the same time as the chemical sensitizer. It is more preferable to perform it beforehand.

The amount of addition was 4 × / mol of silver halide.
It can be used in an amount of from 10 ^-6 to 8 × 10 ^-3 mol. In the case of a more preferable silver halide grain size of 0.2 to 1.2 μm, about 5 × 10 ^-5 to 2 × 10 ^-3 mol is more effective. It is.

The above-mentioned various additives are used in the emulsion according to the present invention. In addition, various additives can be used according to the purpose.

These additives are described in more detail in Research Disclosure Item 17643 (December 1978) and Item 18716 (November 1979).
Mon) and Item 308119 (December 1989)
), And the relevant locations are summarized in Table 1 below.

The light-sensitive material of the present invention comprises a light-sensitive silver halide emulsion having a grain size, a grain size distribution, a halogen composition,
Two or more emulsions differing in at least one characteristic of grain shape and sensitivity can be mixed and used in the same layer.

The fogged silver halide grains described in US Pat. No. 4,082,553, and the inside of the grains described in US Pat. No. 4,626,498 and JP-A-59-214852 are covered. Silver halide grains and colloidal silver can be preferably used for a light-sensitive silver halide emulsion layer and / or a substantially light-insensitive hydrophilic colloid layer.
The term "silver halide particles having a fogged inside or surface thereof" means silver halide grains which can be uniformly (non-imagewise) developed regardless of unexposed portions and exposed portions of the photosensitive material. . A method for preparing silver halide grains having the inside or the surface of the grains fogged is described in U.S. Pat. No. 4,626,498 and JP-A-59-214852.

The silver halide forming the internal nucleus of the core / shell type silver halide grains whose inside is fogged may have the same halogen composition or different halogen compositions. As the silver halide having the inside or surface of the grain fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. There is no particular limitation on the grain size of these fogged silver halide grains, but the average grain size is 0.01 to 0.7.
5 μm, particularly preferably 0.05 to 0.6 μm, is preferred. Also,
The grain shape is not particularly limited, and may be regular grains or polydispersed emulsions, but may be monodispersed (at least 95% of the weight or the number of silver halide grains is within ± 40% of the average grain size). Having a particle size of 1).

In the present invention, it is preferable to use non-photosensitive fine grain silver halide. Non-photosensitive fine grain silver halide is silver halide fine grains that are not exposed during imagewise exposure to obtain a dye image and are not substantially developed in the developing process, and are preferably not fogged in advance. .

The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may contain silver chloride and / or
Alternatively, it may contain silver iodide. Preferably, it contains 0.5 to 10 mol% of silver iodide.

The fine grain silver halide preferably has an average grain size (average value of the equivalent circle diameter of the projected area) of 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm.

The fine grain silver halide can be prepared in the same manner as in the case of ordinary light-sensitive silver halide. In this case, the surface of the silver halide grains does not need to be chemically sensitized,
Also, spectral sensitization is not required. However, prior to adding this to the coating solution, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, or mercapto-based compound or a zinc compound in advance. Colloidal silver can be preferably contained in the layer containing fine silver halide grains.

The amount of silver applied to the light-sensitive material of the present invention is 6.0 g.
/ M ² or less are preferred, 4.5 g / m ² or less is most preferred.

Known photographic additives that can be used in the present invention are also described in the above three Research Disclosures, and the relevant portions are shown in Table 1 below.

Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, US Pat.
It is preferable to add a compound capable of being fixed by reacting with formaldehyde described in JP-A No. 7 or 4,435,503 to the photosensitive material.

The light-sensitive material of the present invention may be added to US Pat.
0,454, 4,788,132, JP-A-62
It is preferable to include a mercapto compound described in JP-A-18539 and JP-A-1-283551.

The light-sensitive material of the present invention may be prepared by the method described in JP-A-1-1060.
No. 52, it is preferable to contain a compound which releases a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof irrespective of the amount of developed silver produced by the development processing.

The light-sensitive material of the present invention may be added to International Publication WO 88 /
Dyes or EP 317,308A dispersed by the method described in JP-A-04794, JP-T-Hei 1-502912.
No. 4,420,555, JP-A-1-259
No. 358 is preferably contained.

Various color couplers can be used in the present invention, and specific examples thereof are described in Research Disclosure No. Nos. 17643, VII-CG and No. 307105, VII-CG.

As the yellow coupler, for example, US Pat. Nos. 3,933,501 and 4,022,620
No. 4,326,024 and 4,401,75
No. 2, No. 4,248,961, Japanese Patent Publication No. 58-107
No. 39, British Patent Nos. 1,425,020 and 1,4
No. 76,760; U.S. Pat. Nos. 3,973,968; 4,314,023; 4,511,649;
Those described in EP 249,473A and the like are preferred.

As the magenta coupler, 5-pyrazolone-based and pyrazoloazole-based compounds are preferable, and US Pat. Nos. 4,310,619 and 4,351,897.
No. 3,073,636; U.S. Pat.
No. 1,432, No. 3,725,067, Research
Disclosure No. 24220 (June 1984
), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, JP-A-61-72238, and JP-A-60-72238.
-35730, 55-118034, 60-1
No. 85951, U.S. Pat. Nos. 4,500,630, 4,540,654, 4,556,630, and WO88 / 04795 are particularly preferable.

Examples of the cyan coupler include phenol type and naphthol type couplers.
No. 52,212, No. 4,146,396, No. 4,
Nos. 228,233, 4,296,200, 2,369,929, 2,801,171, 2,772,162, 2,895,826,
No. 3,772,002 and No. 3,758,308
No. 4,343,011, No. 4,327,17
3, West German Patent Publication No. 3,329,729, European Patent Nos. 121,365A and 249,453A, U.S. Patent Nos. 3,446,622 and 4,333,999.
No. 4,775,616, No. 4,451,55
No. 9, No. 4,427,767, No. 4,690, 8
No. 89, No. 4,254,212, No. 4,296,
199 and JP-A-61-42658 are preferred.

Typical examples of polymerized dye-forming couplers are described in US Pat. Nos. 3,451,820 and 4,082.
No. 0,211, No. 4,367,282, No. 4,4
Nos. 09,320, 4,576,910, British Patent 2,102,137, and European Patent No. 341,188A.

Examples of couplers in which a coloring dye has an appropriate diffusibility include US Pat. No. 4,366,237, British Patent No. 2,125,570, and European Patent No. 96,570.
Those described in West German Patent (Published) No. 3,234,533 are preferred.

A colored coupler for correcting unnecessary absorption of a coloring dye is available from Research Disclosure N
o. No. 17643, section VII-G; 307105
Section VII-G, U.S. Pat. No. 4,163,670, JP-B-57-39413, U.S. Pat. No. 4,004,929.
No. 4,138,258 and British Patent No. 1,14.
No. 6,368 is preferred. In addition, a coupler described in U.S. Pat. No. 4,774,181 for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling, or reacting with a developing agent described in U.S. Pat. No. 4,777,120. It is also preferable to use a coupler having a dye precursor group capable of forming a dye as a leaving group.

Compounds which release a photographically useful residue upon coupling can also be preferably used in the present invention.
The DIR coupler releasing a development inhibitor is described in RD.
No. 17643, VII-F and the same No. 307105, V
Patents described in section II-F, JP-A-57-151944
No., No. 57-154234, No. 60-184248
And JP-A-63-37346 and JP-A-63-37350, and U.S. Pat. Nos. 4,248,962 and 4,782,012 are preferred.

Examples of couplers which release a nucleating agent or a development accelerator in an image-like manner during development include British Patent No. 2,099.
7,140,2,131,188, JP-A-59
Preferred are those described in JP-A-157638 and JP-A-59-170840. Also, JP-A-60-107029, JP-A-60-252340, JP-A-1-44940 and JP-A-1-44940.
Also preferred are compounds capable of releasing a fogging agent, a development accelerator, a silver halide solvent and the like by an oxidation-reduction reaction with an oxidized form of a developing agent described in JP-A-45687.

Other compounds that can be used in the light-sensitive material of the present invention include US Pat. No. 4,130,427.
No. 4,283,4.
No. 72, No. 4,338,393, No. 4,310,
No. 618, etc .;
No. 5950, Japanese Patent Application Laid-Open No. 62-24252, and the like.
R redox compound releasing couplers, DIR coupler releasing couplers, DIR coupler releasing redox compounds or DIR redox releasing redox compounds, couplers capable of releasing dyes which discolor after release as described in EP 173,302A and EP 313,308A , R.A. D. N
o. 11449, 24241, JP-A-61-2012
No. 47, a bleach accelerator releasing coupler described in U.S. Pat. No. 4,555,477, a leuco dye releasing coupler described in JP-A-63-75747, U.S. Pat. And couplers which release a fluorescent dye described in U.S. Pat.

The coupler used in the present invention can be introduced into a light-sensitive material by various known dispersion methods.

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

Specific examples of the high-boiling organic solvent having a boiling point at normal pressure of 175 ° C. or higher used in the oil-in-water dispersion method include phthalic acid esters (for example, dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, Decyl phthalate, bis (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate), phosphoric acid or phosphone Acid esters (e.g., triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2
-Ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenylphosphonate), benzoates (eg, 2-ethylhexyl benzoate), dodecyl benzoate,
-Ethylhexyl-p-hydroxybenzoate), amides (eg, N, N-diethyldodecaneamide,
N-diethyllaurylamide, N-tetradecylpyrrolidone), alcohols or phenols (eg, isostearyl alcohol, 2,4-di-tert-amylphenol), aliphatic carboxylic acid esters (eg, bis (2-ethylhexyl)) Sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate), aniline derivatives (for example, N, N-dibutyl-2-butoxy-5-te)
rt-octylaniline), hydrocarbons (eg, paraffin, dodecylbenzene, diisopropylnaphthalene)
And the like. The auxiliary solvent has a boiling point of about 3
An organic solvent having a temperature of 0 ° C. or more, preferably 50 ° C. or more and about 160 ° C. or less can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, and dimethylformamide. Can be

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,3.
No. 63, West German Patent Application (OLS) No. 2,541,274
And No. 2,541,230.

In the photographic light-sensitive material of the present invention, phenethyl alcohol, JP-A-63-257747 and JP-A-62-274 can be used.
No. 72248 and JP-A-1-80941, 1,2-benzisothiazolin-3-one, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol, It is preferable to add various preservatives or fungicides such as-(4-thiazolyl) benzimidazole.

The present invention can be applied to various photographic materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films, and color reversal papers.

Suitable supports that can be used in the present invention are described, for example, in RD. No. No. 17643, page 28;
No. 18716, from the right column on page 647 to the left column on page 648; 307105, page 879.

In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, and 18 μm or less.
m or less, more preferably 16 μm or less.
Further, the film swelling speed T _1/2 is preferably 30 seconds or less, and more preferably 20 seconds or less. The film thickness means a film thickness measured at 25 ° C. and a relative humidity of 55% (2 days), and the film swelling speed T
_1/2 can be measured according to techniques known in the art. For example, A. Gr.
een) et al. in Photographic Science and Engineering (Photogr. Sci. E).
ng. ), Vol. 19, No. 2, pp. 124-129 can be measured by using a type of serometer (swelling meter), and T _1/2 is treated with a color developing solution at 30 ° C. for 3 minutes and 15 seconds. 90% of the maximum swelled film thickness that is reached when the swelling is performed is defined as the saturated film thickness, and defined as the time required to reach 1/2 of the saturated film thickness.

The film swelling speed T _1/2 can be adjusted by giving a hardening agent to gelatin as a binder or by changing the aging conditions after coating. The swelling ratio is preferably from 150 to 400%. The swelling ratio is calculated from the maximum swelling film thickness under the conditions described above by the following formula:
It can be calculated according to (maximum swollen film thickness-film thickness) / film thickness.

In the light-sensitive material of the present invention, a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm is preferably provided on the side opposite to the side having the emulsion layer. The back layer preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, surface active agent, and the like. The swelling ratio of this back layer is 150
~ 500% is preferred.

The color photographic light-sensitive material according to the present invention is prepared according to the RD. No. No. 17643, pages 28 to 29;
No. 18716, 651 left column to right column; 307
105, pages 880-881.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution mainly containing an aromatic primary amine-based color developing agent. Aminophenol compounds are also useful as the color developing agent, but p-phenylenediamine compounds are preferably used, and a typical example thereof is 3-methyl-4-amino-
N, N diethylaniline, 3-methyl-4-amino-N
-Ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N
-Ethyl-β-methoxyethylaniline and sulfates, hydrochlorides or p-toluenesulfonates thereof. Among these, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline sulfate is particularly preferred. These compounds can be used in combination of two or more depending on the purpose.

The color developing solution may be a pH buffer such as an alkali metal carbonate, borate or phosphate, a chloride, a bromide, an iodide, a benzimidazole, a benzothiazole or a mercapto compound. It generally contains such a development inhibitor or antifoggant. If necessary, various preservatives such as hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazide, triethanolamine, catecholsulfonic acid, ethylene glycol, Organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting Agents, aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, various chelating agents represented by phosphonocarboxylic acid, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cycloalkyl Hexane diamine tetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene--
1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N
-Tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof can be mentioned as typical examples.

When the reversal process is performed, color development is usually performed after black and white development. A known black-and-white developing agent such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone or aminophenols such as N-methyl-p-aminophenol is used alone in the black-and-white developer. Alternatively, they can be used in combination.

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

The contact area between the photographic processing solution and air in the processing tank can be represented by the aperture ratio defined below.

That is, opening ratio = contact area (cm ² ) between processing solution and air / capacity of processing solution (cm ³ ) The above opening ratio is preferably 0.1 or less, more preferably 0.1% or less. 001 to 0.05. As a method of reducing the aperture ratio in this manner, in addition to providing a shield such as a floating lid on the surface of the photographic processing solution in the processing tank, Japanese Patent Application Laid-Open No.
No. 033, a method using a movable lid,
And a slit developing method described in JP-A-216050. Reducing the aperture ratio is not only in both the color development and black-and-white development steps, but also in the subsequent steps,
For example, it is preferably applied in all steps such as bleaching, bleach-fixing, fixing and stabilization. The amount of replenishment can also be reduced by using means for suppressing the accumulation of bromide ions in the developer.

The time for the color development processing is usually set to 2 to 5 minutes. However, the processing time can be further shortened by using a high temperature and high pH and using a high concentration of the color developing agent. it can.

The photographic emulsion layer after color development is usually subjected to bleaching. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. In order to further speed up the processing, a processing method of performing bleach-fixing after bleaching may be used. Further, processing in two successive bleach-fixing baths, fixing before bleach-fixing, or bleaching after bleach-fixing can be arbitrarily performed according to the purpose. As the bleaching agent, for example, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds and the like are used. Typical bleaching agents are organic complex salts of iron (III),
For example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, and glycol ether diaminetetraacetic acid, or complex salts such as citric acid, tartaric acid, and malic acid. Etc. can be used. Of these, iron (III) complex salts of aminopolycarboxylic acid such as iron (III) complex salt of ethylenediaminetetraacetate and iron (III) complex salt of 1,3-diaminopropanetetraacetate are preferable from the viewpoint of rapid treatment and prevention of environmental pollution. . Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in a bleaching solution and a bleach-fixing solution. The pH of the bleaching solution or the bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually from 4.0 to 8, but the processing can be carried out at a lower pH in order to speed up the processing.

In the bleaching solution, the bleach-fixing solution and the prebath thereof, a bleaching accelerator can be used if necessary.
Specific examples of useful bleach accelerators are described in the following specification: U.S. Pat. No. 3,893,858, West German Patent Nos. 1,290,812, 2,059,988, JP Nos. 53-32736, 53-57831, 53
No. 37418, No. 53-72623, No. 53-95
No. 630, No. 53-95731, No. 53-10423
No. 2, No. 53-124424, No. 53-141623
No. 53-28426, Research Disclosure No. Compounds having a mercapto group or a disulfide group described in No. 17129 (July, 1978);
Thiazolidine derivatives described in JP-A-50-140129; JP-B-45-8506; JP-A-52-20832.
No. 53-32735, U.S. Pat. No. 3,706,5
No. 61; thiourea derivative; West German Patent No. 1,12
7,715; iodide salts described in JP-A-58-16235; West German Patent Nos. 966,410 and 2,748,
No. 430; polyamine compounds described in JP-B-45-8836; and JP-A-49-40,943; JP-A-49-59,644; JP-A-53-94,927; 54-35,727, 5
Compounds described in Nos. 5-26,506 and 58-163,940; bromide ions and the like can be used. Among them, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large accelerating effect, and in particular, US Pat.
No. 858, West German Patent No. 1,290,812,
Compounds described in 3-95,630 are preferred. Furthermore,
The compounds described in U.S. Pat. No. 4,552,834 are also preferred. These bleaching accelerators may be added to the light-sensitive material.
These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography.

The bleaching solution and the bleach-fixing solution preferably contain an organic acid in addition to the above compounds for the purpose of preventing bleaching stain. Particularly preferred organic acids are compounds having an acid dissociation constant (pKa) of 2 to 5, specifically acetic acid,
Propionic acid and the like are preferred.

Examples of the fixing agent used in the fixing solution or the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodides. Is common, and in particular, ammonium thiosulfate can be used most widely. It is also preferable to use a combination of a thiosulfate and a thiocyanate, a thioether-based compound, thiourea, or the like. As a preservative of the fixing solution or the bleach-fixing solution, a sulfite, a bisulfite, a carbonyl bisulfite adduct, or a sulfinic acid compound described in EP-A-294769A is preferable. Further, it is preferable to add various aminopolycarboxylic acids or organic phosphonic acids to the fixing solution or the bleach-fixing solution for the purpose of stabilizing the solution.

In the present invention, the fixing solution or the bleach-fixing solution contains a compound having a pKa of 6.0 to 9.0, preferably imidazole, 1-methylimidazole, 1-ethylimidazole, It is preferable to add imidazoles such as methyl imidazole in an amount of 0.1 to 10 mol / l.

The total time of the desilvering step is preferably as short as possible without desilvering failure. Preferred time is 1 minute to 3
Minutes, more preferably 1 to 2 minutes. Further, the processing temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C.
In a preferable temperature range, the desilvering speed is improved, and generation of stain after processing is effectively prevented.

In the desilvering step, it is preferable that the stirring is strengthened as much as possible. As a specific method of strengthening the stirring, a method described in JP-A-62-183460, in which a jet of a processing solution is made to impinge on the emulsion surface of a photosensitive material, or a method using a rotating means described in JP-A-62-183461, is used. A method of increasing the effect, a method of moving the photosensitive material while bringing the wiper blade provided in the solution into contact with the emulsion surface, and increasing the stirring effect by turbulently flowing the emulsion surface, and circulating the entire processing solution. There is a method of increasing the flow rate. Such stirring improving means include a bleaching solution, a bleach-fixing solution,
It is effective in any of the fixing solutions. It is considered that improving the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, and consequently increases the desilvering speed. Further, the above-described means for improving the stirring is more effective when a bleaching accelerator is used, and can significantly increase the accelerating effect or eliminate the fixing inhibiting effect of the bleaching accelerator.

The automatic developing machine used for the light-sensitive material of the present invention is disclosed in JP-A-60-191257 and JP-A-60-19125.
No. 8, No. 60-191259. JP-A-60-1
As described in JP-A-91257, such a transporting means can significantly reduce the carry-in of the processing liquid from the pre-bath to the post-bath, and is highly effective in preventing the performance of the processing liquid from deteriorating. Such an effect is particularly effective for reducing the processing time in each step and reducing the replenishing amount of the processing solution.

The silver halide color photographic light-sensitive material of the present invention generally undergoes a washing and / or stabilizing step after desilvering. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, the material used such as a coupler), the use, the rinsing water temperature, the number of rinsing tanks (number of stages), the replenishment method such as countercurrent, forward flow, and other various conditions. Can be set widely.
Among them, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent method is described in Journal of the Society.
y of Motion Picture and T
Evolution Engines Vol. 64,
P. 248-253 (May, 1955).

According to the multi-stage counter-current method described in the above document,
Although the amount of washing water can be greatly reduced, the increase in the residence time of the water in the tank causes a problem that bacteria proliferate and generated floating substances adhere to the photosensitive material. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method of reducing calcium ions and magnesium ions described in JP-A-62-28838 can be used very effectively. Also, Japanese Unexamined Patent Publication No.
No.-8,542, isothiazolone compounds, thiabendazoles, chlorinated bactericides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., written by Hiroshi Horiguchi, "Chemistry of Fungicides and Fungicides" (1986) Sankyo Publishing, Sanitary Technology Society, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982
The fungicide described in "Encyclopedia of Bactericidal and Fungicides" (ed. 1986), edited by the Japan Society of Bacteria and Fungi.

The pH of the washing water in the processing of the light-sensitive material of the present invention is from 4 to 9, preferably from 5 to 8. The washing temperature and washing time can also be variously set depending on the characteristics of the photosensitive material, the use, etc., but are generally at 15 to 45 ° C. for 20 seconds to 10 minutes,
Preferably, a range of 30 seconds to 5 minutes at 25 to 40 ° C is selected. Further, the light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the above-mentioned water washing. In such a stabilizing process, JP-A-57-8543 and JP-A-58-8543 are used.
All known methods described in JP-A-14834 and JP-A-60-220345 can be used.

In some cases, a stabilization treatment may be performed after the water washing treatment. For example, a stabilization treatment containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photography, may be used. Baths can be mentioned. Examples of the dye stabilizer include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts.

Various chelating agents and fungicides can be added to this stabilizing bath.

The overflow solution accompanying the washing and / or replenishment of the stabilizing solution can be reused in other steps such as a desilvering step.

In the processing using an automatic developing machine or the like, when the above-mentioned processing solutions are concentrated by evaporation, it is preferable to correct the concentration by adding water.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up the processing. In order to incorporate the color developing agent, it is preferable to use various precursors of a color developing agent. For example, U.S. Pat.
No. 342,597, indoaniline compounds, and No. 3,342,599, Research Disclosure No. 14, 850 and the same No. 15, 159, Schiff base compounds, aldol compounds described in 13,924, metal salt complexes described in U.S. Pat. No. 3,719,492, and urethane-based compounds described in JP-A-53-135628. be able to.

The silver halide color light-sensitive material of the present invention comprises
If necessary, various 1-
Phenyl-3-pyrazolidones may be incorporated. Typical compounds are described in JP-A-56-64339 and JP-A-57-14.
Nos. 4547 and 58-115438.

Various processing solutions in the present invention may be used at a temperature of 10 ° C. to 50 ° C.
Used at ° C. Usually, a temperature of 33 ° C. to 38 ° C. is standard, but a higher temperature promotes the processing and shortens the processing time, and a lower temperature achieves an improvement in the image quality and an improvement in the stability of the processing solution. be able to.

The silver halide light-sensitive material of the present invention is disclosed in US Pat. No. 4,500,626 and JP-A-60-1334.
No. 49, 59-218443, 61-23805
No. 6, EP 210,660 A2 and the like.

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

Example 1 Preparation of Emulsion A Aqueous gelatin solution [H ₂ O 1200 cc, empty
y Contains 6 g of gelatin and 0.5 g of NaCl, pH 9.
0], the temperature was brought to 65 ° C., and AgNO was
₃ solution (0.1 g / cc) and NaCl solution (0.0345 g /
(cc) at 15 cc / min for 12 minutes. Next, a gelatin solution [H ₂ O 100 cc, gelatin 19 g,
NaCl (1.3 g) was added, and a 1N HNO ₃ solution was added to adjust the pH to 4.0. Then raise the temperature to 70 ° C and
After ripening for 6 minutes, 0.9 mol of a fine grain emulsion (A) described below was added in an Ag amount. After ripening for 35 minutes, 0.05 mol of the fine grain emulsion (A) was added and ripened for 5 minutes.

Then, the temperature was lowered to 35 ° C., and the emulsion was washed with water by a sedimentation washing method according to a conventional method. Then, an aqueous gelatin solution was added, the temperature was raised to 40 ° C., and the pH of the emulsion was adjusted to 6.4 and pCl
Adjusted to 2.8. The emulsion was collected and a TEM image was observed. According to the result, the emulsion A had a {100} major plane, and the tabular grains having an average grain size of 1.4 μm and an average aspect ratio of 6.5 accounted for 80% of the projected area of all AgX grains.
Was occupied. (Preparation of Fine Particle Emulsion (A)) An aqueous gelatin solution [1200 cc of H ₂ O, gelatin having an average molecular weight of 30,000 (M
3) 24 g, containing 0.5 g of NaCl, pH 3.0]
While stirring at a temperature of 23 ° C. while stirring the AgNO ₃ solution (A
gNO ₃ 0.2g / cc, M3 0.01g / cc, HNO
₃ 0.1N 0.25cc / 100cc) and NaCl solution (NaCl 0.07g / cc, M3 0.01g / cc,
KOH1N solution 0.25cc / 100cc)
For 9 minutes. After stirring for 1 minute, p
H 4.0, adjusted to pCl 1.7.

Preparation of Emulsion B After the ripening, the same procedure as in the preparation of Emulsion A was performed until the fine grain emulsion (A) was added in an amount of 0.9 mol in terms of Ag and ripened for 35 minutes. Next, a fine grain emulsion (B) described later was added in an Ag amount of 0.05
Mol was added and aged for 5 minutes. Thereafter, the preparation was the same as in the preparation of emulsion A.

The obtained emulsion B had a {100} major plane, an average grain size of 1.4 μm, and an average aspect ratio of 6.5 tabular grains having a projected area of 79% of the total AgX grains.
Accounted for%. Analysis by XPS revealed that the silver iodide content on the grain surface was 1.5 mol%. (Preparation of Fine Particle Emulsion (B)) An aqueous gelatin solution [1200 cc of H ₂ O, 24 g of M3, 0.5 g of NaCl
g, pH 3.0], and stirred at a temperature of 23 ° C. while stirring the AgNO ₃ solution (AgNO ₃ 0.2 g / cc, M3
0.01g / cc, HNO ₃ 1N 0.25cc / 100cc
And NaCl solution (NaCl 0.07 g / cc, K
I 0.004 / g / cc, M3 0.01 g / cc, K
OH1N solution (including 0.25 cc / 100 cc) at 90 cc / min for 3 minutes. After stirring for 1 minute, pH
4.0, adjusted to pCl 1.7.

Preparation of Emulsion C After the ripening, the same procedure as in the preparation of Emulsion A was carried out until the fine grain emulsion (A) was added in an amount of 0.9 mol of Ag and ripened for 35 minutes. Next, a fine grain emulsion (C) described later was added in an Ag amount of 0.05
Mol was added and aged for 5 minutes. Thereafter, the preparation was the same as in the preparation of emulsion A.

Emulsion C thus obtained had a {100} major plane, an average grain size of 1.4 μm, and an average aspect ratio of 6.3 tabular grains having a projected area of 77% of the total AgX grains.
Accounted for%. As a result of analysis by XPS, it was found that the silver iodide content on the grain surface was 4.1 mol%. (Preparation of Fine Particle Emulsion (C)) An aqueous gelatin solution (1200 cc of H ₂ O, 24 g of M3, 0.5 g of NaCl) was placed in a reaction vessel.
g, pH 3.0], and stirred at a temperature of 23 ° C. while stirring the AgNO ₃ solution (AgNO ₃ 0.2 g / cc, M3
0.01g / cc, HNO ₃ 1N 0.25cc / 100cc
And NaCl solution (NaCl 0.07 g / cc, K
I 0.0105 / g / cc, M3 0.01 g / cc,
KOH1N solution 0.25cc / 100cc)
For 3 minutes. After stirring for 1 minute, p
H 4.0, adjusted to pCl 1.7.

Preparation of Emulsion D An aqueous gelatin solution [H ₂ O 1200 cc, empty
y Contains 6 g of gelatin and 0.5 g of NaCl, pH 9.
0], the temperature was brought to 65 ° C., and AgNO was
₃ solution (0.1 g / cc) and NaCl solution (NaCl 0.0
(345 g / cc, KI containing 0.0020 g / cc) at 15 cc / min for 12 minutes. Next, a gelatin solution [H ₂ O 100 cc, gelatin 19 g, NaC
l 1.3 g], HNO ₃ 1N solution was added,
pH was adjusted to 4.0. Next, the temperature was raised to 70 ° C., and after ripening for 16 minutes, 0.9 mol of a fine grain emulsion (A) in an Ag amount was added. Thereafter, the preparation was the same as in the preparation of emulsion A.

Emulsion D thus obtained had {100} major planes, an average grain size of 1.2 μm, and an average aspect ratio of 6.1 tabular grains having a projected area of 77% of the total AgX grains.
Accounted for%.

Emulsions A to D at 60 ° C., pH 6.2
Under the conditions of 0 and pAg 8.40, the following chemical sensitization was performed.

First, a sensitizing dye represented by the following chemical formula 1 was added in an amount of 1.6 × 10 ^-3 mol per mol of silver.

Subsequently, 3.0 × 10 ^-3 per mol of silver
Moles of potassium thiocyanate, 6 × 10 ⁻⁶ moles of potassium chloroaurate, 1 × 10 ⁻⁵ moles of sodium thiosulfate and selenium sensitizer represented by the following formula (2) in an amount of 3 × 10 6 moles per mole of silver halide. Add ⁶ mol and ripen at 60 ° C, 1/1
The ripening time was adjusted so that the sensitivity of the exposure for 00 seconds was the highest.

After completion of the chemical sensitization, the following compounds were added, and coated on a triacetyl cellulose film support having an undercoat layer together with a protective layer by a simultaneous extrusion method so that the silver amount was 0.5 g / m ^2. did. (1) Emulsion layer Emulsion Emulsions A to D Compound 1 represented by the following structural formula shown in Chemical Formula 3 below Tricresyl phosphate Stabilizer 4-hydroxy-6-methyl-1,3,3 3
a, 7-Tetrazaindene ・ Coating aid sodium dodecylbenzenesulfonate (2) Protective layer ・ Polymethyl methacrylate fine particles ・ Sodium 2,4-dichloro-6-hydroxy-s-triazine sodium salt ・ Gelatin Exposure for metrology (1/100
Sec), and the following color development processing was performed.

The development processing used here was performed at 38 ° C. under the following conditions.

1. Color development: 2 minutes 45 seconds Bleaching: 6 minutes and 30 seconds 3. Rinse ... 3 minutes 15 seconds 4. Fixed arrival: 6 minutes 30 seconds 5. Rinse ... 3 minutes 15 seconds 6. Stability: 3 minutes 15 seconds The treatment composition used in each step is as follows. Color developer Sodium nitrilotriacetate 1.0 g Sodium sulfite 4.0 g Sodium carbonate 30.0 g Potassium bromide 1.4 g Hydroxylamine sulfate 2.4 g 4- (N-ethyl-N-βhydroxyethylamino) -2- Methyl-aniline sulfate 4.5 g 1 liter after adding water 1 liter Bleaching solution Ammonium bromide 160.0 g ammonia water (28%) 25.0 ml ethylenediamine-tetraacetic acid sodium salt 130 g glacial acetic acid 14 ml Add water to fix 1 liter Liquid Sodium tetrapolyphosphate 2.0 g Sodium sulfite 4.0 g Ammonium thiosulfate (70%) 175.0 ml Sodium bisulfite 4.6 g 1 liter with water Stabilized solution Formalin 8.0 ml 1 liter with water Was measured for density with a green filter.

The sensitivity was defined as the reciprocal of the exposure amount giving a density of fog + 0.1, and expressed as a relative value with the value of sample 1 being 100. The sensitivity values are shown in Table 2 below.

Table 2 shows that the silver halide emulsion according to the present invention has high sensitivity.

Example 2 On a subbed cellulose triacetate film support,
Each layer having the composition shown below was applied in multiple layers to prepare a sample 101 as a multilayer color photosensitive material. (Composition of photosensitive layer) The main materials used for each layer are classified as follows: ExC: cyan coupler UV: ultraviolet absorber ExM: magenta coupler HBS: high boiling point organic solvent ExT: yellow coupler H: gelatin Curing agent ExS: Sensitizing dye The number corresponding to each component indicates the coating amount in g / m ² , and for silver halide, it indicates the coating amount in terms of silver. However, as for the sensitizing dye, the coating amount is shown in mol unit with respect to 1 mol of silver halide in the same layer. (Sample 101) First Layer (Antihalation Layer) Black Colloidal Silver Silver 0.18 Gelatin 1.40 ExM-1 0.18 ExF-1 2.0 × 10 ^-3 HBS-1 0.20 Second Layer (Intermediate) Layer) Emulsion Q silver 0.065 2,5-di-t-pentadecylhydroquinone 0.18 ExC-2 0.020 UV-1 0.060 UV-2 0.080 UV-3 0.10 HBS-10 .10 HBS-2 0.020 Gelatin 1.04 Third layer (low-sensitivity red-sensitive emulsion layer) Emulsion K silver 0.25 Emulsion L silver 0.25 ExS-1 6.9 × 10 ^-5 ExS-2 8 × 10 ^-5 ExS-3 3.1 × 10 ^-4 ExC-1 0.17 ExC-3 0.030 ExC-4 0.10 ExC-5 0.020 ExC-7 0.0050 ExC-8 010 Cpd-2 0.025 HBS- 0.10 Gelatin 0.87 Fourth Layer (medium-sensitivity red-sensitive emulsion layer) Emulsion N silver ^{0.70 ExS-1 3.5 × 10 -4} ExS-2 1.6 × 10 -5 ExS-3 5.1 × 10 ^-4 ExC-1 0.13 ExC-2 0.060 ExC-3 0.0070 ExC-4 0.090 ExC-5 0.025 ExC-7 0.0010 ExC-8 0.0070 Cpd-20 0.023 HBS-1 0.10 Gelatin 0.75 Fifth layer (high-sensitivity red-sensitive emulsion layer) Emulsion O Silver 1.40 ExS-1 2.4 × 10 ^-4 ExS-2 1.0 × 10 ^-4 ExS -3 3.4 × 10 ^-4 ExC-1 0.12 ExC-3 0.045 ExC-6 0.020 ExC-8 0.025 Cpd-2 0.050 HBS-1 0.22 HBS-2 10 gelatin 1.20 6th layer (middle layer) Cpd-10 10 HBS-1 0.50 Gelatin 1.10 7th layer (low sensitivity green-sensitive emulsion layer) Emulsion M silver ^{0.35 ExS-4 3.0 × 10 -5} ExS-5 2.1 × 10 -4 ExS- 6 8.0 × 10 ^-4 ExM-1 0.010 ExM-2 0.33 ExM-3 0.086 ExY-1 0.015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.73 8th Layer (Medium Speed Green Sensitive Emulsion Layer) Emulsion N Silver 0.80 ExS-4 3.2 × 10 ^-5 ExS-5 2.2 × 10 ^-4 ExS-6 8.4 × 10 ^-4 ExM-20. 13 ExM-3 0.030 ExY-1 0.018 HBS-1 0.16 HBS-3 8.0 × 10 ^-3 gelatin 0.90 9th layer (high-sensitivity green-sensitive emulsion layer) Emulsion A (Example 1) Silver 1.25 ExC-1 0.010 ExM-1 0.030 ExM-4 0.0 0 ExM-5 0.019 Cpd-3 0.040 HBS-1 0.25 HBS-2 0.10 Gelatin 1.44 10th layer (yellow filter layer) Yellow colloidal silver Silver 0.030 Cpd-1 0.16 HBS-1 0.60 Gelatin 0.60 Eleventh layer (low-sensitivity blue-sensitive emulsion layer) Emulsion M Silver 0.18 ExS-7 8.6 × 10 ^-4 ExY-1 0.020 ExY-2 0.22 ExY -3 0.50 ExY-4 0.020 HBS-1 0.28 Gelatin 1.10 12th layer (Medium speed blue-sensitive emulsion layer) Emulsion N silver 0.40 ExS-7 7.4 × 10 ^-4 ExC- 7 7.0 × 10 ^-3 ExY-2 0.050 ExY-3 0.10 HBS-1 0.050 Gelatin 0.78 13th layer (high-sensitivity blue-sensitive emulsion layer) Emulsion P Silver 1.00 ExS-7 4.0 × 10 ^-4 ExY-2 .10 ExY-3 0.10 HBS-1 0.070 Gelatin 0.86 Fourteenth layer (first protective layer) Emulsion Q silver 0.20 UV-4 0.11 UV-5.17 HBS-1 5. 0 × 10 ^-2 gelatin 1.00 Fifteenth layer (second protective layer) H-1 0.40 B-1 (1.7 μm in diameter) 5.0 × 10 ^-2 B-2 (1.7 μm in diameter) 0 .10 B-3 0.10 S-1 0.20 Gelatin 1.20 Furthermore, the respective layers may be appropriately preserved, processed, pressure-resistant, and mildew-proof.
In order to improve antibacterial properties, antistatic properties and coatability, W-
1 to W-3, B-4 to B-6, F-1 to F
-17 and iron, lead, gold, platinum, iridium and rhodium salts.

The emulsions used are shown in Table 3 below. The structural formulas of the components of each layer are shown in Chemical Formulas 4 to 18 below.

In Table 3, (1) Emulsions K to P were subjected to reduction sensitization during the preparation of grains using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-191938. (2) Emulsions K to P were subjected to gold sensitization, sulfur sensitization and selenium sensitization in the presence of the spectral sensitizing dye and sodium thiocyanate described in each photosensitive layer according to the examples of JP-A-3-237450. Have been. (3) For preparing tabular grains, low molecular weight gelatin is used according to the examples of JP-A-1-158426. (4) Dislocation lines as described in JP-A-3-237450 are observed in tabular grains and normal crystal grains having a grain structure using a high-pressure electron microscope.

By changing the emulsion of the ninth layer (high-sensitivity green-sensitive emulsion layer) from Emulsion A to Emulsions BD, Samples 102 to 102 were obtained.
104 were produced.

Each of the samples 101 to 104 was exposed to sensitometry (1/100 second) and processed by the method described below. (Processing method) Process Processing time Processing temperature Color development 3 minutes 15 seconds 38 ° C Bleaching 6 minutes 30 seconds 38 ° C Rinse 2 minutes 10 seconds 24 ° C Fixed 4 minutes 20 seconds 38 ° C Rinse (1) 1:05 seconds 24 ° C. Water washing (2) 1 minute 00 seconds 24 ° C. Stabilization 1 minute 05 seconds 38 ° C. Drying 4 minutes 20 seconds 55 ° C. Next, the composition of the processing solution is shown. (Color developing solution) (unit: g) Diethylenetriaminepentaacetic acid 1.0 1-hydroxyethylidene-1,1-diphosphonic acid 3.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 5 mg hydroxylamine sulfate 2.4 4- (N-ethyl-N-β-hydroxyethylamino) -2-methylaniline sulfate 4.5 Water was added to make 1.0 liter pH 10.05 (bleach solution) ( Unit g) Sodium ferric ethylenediaminetetraacetate trihydrate 100.0 Ethylenediaminetetraacetic acid disodium salt 10.0 Ammonium bromide 140.0 Ammonium nitrate 30.0 Aqueous ammonia (27%) 6.5 ml Add water 1. 0 liter pH 6.0 (fixing solution) (unit: g) Ethylenediaminetetraacetic acid disodium salt 0.5 Sodium citrate 7.0 Sodium bisulfite 5.0 Ammonium thiosulfate aqueous solution (70%) 170.0 ml Add water 1.0 liter pH 6.7 (Stabilized solution) (g) Formalin (37%) 2.0 ml Poly Oxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 Disodium ethylenediaminetetraacetate 0.05 Add water 1.0 liter pH 5.0-8.0 Regarding characteristic curve of magenta color image From the fog density: 1.
The sensitivity defined by the reciprocal of the exposure amount that gives 0 higher density is represented by a relative value with the value of sample 101 being 100, and Table 4 below
It was shown to.

From Table 4, it can be seen that the use of the emulsion of the present invention has an effect of high sensitivity even in a multilayer-coated sample.

As described above, the silver halide photographic light-sensitive material of the present invention exhibits excellent photographic sensitivity.

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[Table 1]

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[Table 4]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI G03C 1/09 G03C 1/09

Claims (6)

(57) [Claims] 1. Two parallel main planes are {100} planes, the aspect ratio is 2 or more, the average silver chloride content of the grains is 60 mol% or more, and the silver iodide content of the grain surfaces is 1. Silver halide emulsion, wherein tabular silver halide grains having a content of 1 mol% or more occupy 50% or more of the total projected area of the silver halide grains. 2. A silver halide photographic light-sensitive material, wherein at least one silver halide emulsion layer provided on a support contains the silver halide emulsion according to claim 1. 3. The silver halide photographic light-sensitive material according to claim 2, wherein the silver iodide content on the surface of said tabular silver halide grains is 2.5 mol% or more. 4. A silver halide photographic material according to claim 2, wherein said tabular silver halide grains are sensitized with gold and sulfur. 5. The silver halide photographic material according to claim 2, wherein said tabular silver halide grains are spectrally sensitized by a cyanine dye. 6. A silver halide photographic material according to claim 2, wherein said tabular silver halide grains are sensitized with gold and sulfur in the presence of a cyanine dye.