JPH0627575A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To stably obtain a high-quality picture without the sensitivity and quality being fluctuated even by brief processing and having a sharp highlight part. CONSTITUTION:This silver halide photographic sensitive material has at least one silver halide emulsion layer contg. the silver halide grain chemically sensitized by a sulfur sensitizer and a gold sensitizer. The photosensitive silver halide grain is chemically sensitized so that the contribution in sensitization by the sulfur sensitizer to the sensitivity of the emulsion layer when the gold sensitizer is absent is controlled to 20-80% of the sensitivity when the gold sensitizer is present, and at least one kind among group VIII metals, group II transition metals, lead, rhenium, molybdenum, tungsten and chromium is incorporated in the grain and/or on the surface.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material capable of stably obtaining a high-quality image in which highlights are sharply cut even by processing for a short time. Specifically, a silver halide photographic light-sensitive material capable of stably obtaining a high quality image with a sharp cut in the highlight portion regardless of whether the color negative is underexposed or overexposed, and regardless of the length of time from exposure to development. It is about.

[0002]

BACKGROUND OF THE INVENTION In recent years, the printing process and the developing process of a photosensitive material for printing have been shortened and accelerated, and it is strongly demanded that the sensitivity is high and the processing is stable. Is becoming.
Conventionally, a sulfur-sensitized silver chlorobromide grain emulsion has been put to practical use as a light-sensitive material for printing. However, for rapid processing, the silver halide grains have high solubility in water and little development inhibitory action by bromine ions, and a silver halide emulsion containing a high concentration of silver chloride (high silver chloride). Grain emulsion) has come into practical use.

Generally, a high silver chloride grain emulsion consisting of substantially cubic grains having a (100) face is used as a high silver chloride grain emulsion satisfying the requirement of rapidity of development processing. Large rule failure, long exposure with low illumination,
Desensitization by high-intensity short-time exposure, large change in gradation, unstable latent image formed by exposure, high sensitivity is difficult only with sulfur sensitization, gold sensitization alone or gold sensitization It is known that when chemical sensitization that uses both sensitivity and sulfur sensitization is performed, fog is likely to occur, and the like.

On the other hand, it is known that by incorporating a metal compound of Group VIII of the periodic table, reciprocity failure can be improved and high sensitivity can be achieved. In addition, Japanese public examination 4
9-33781, JP-A-50-23618, 52
-18310, 58-15952, 59-21
No. 4028, No. 61-67845 and the like disclose that inclusion of a rhodium compound or an iridium compound can improve reciprocity law failure and increase the contrast.

However, although such a known technique can improve the reciprocity law failure, it has a drawback that sufficient sensitivity cannot be obtained yet, and the latent image in an extremely short time after exposure is formed. It was difficult to obtain a stable finished image because the fluctuations became large and the characteristics such as sensitivity and gradation changed depending on the time from exposure to development. Due to the above situations, rapid development processing suitability, high sensitivity, low fog, small reciprocity law failure, and small fluctuation of latent image are strongly developed. It was requested.

[0006]

SUMMARY OF THE INVENTION The object of the present invention is to provide a silver halide photograph capable of stably obtaining a high-quality image with excellent sharpness in the highlight portion without causing sensitivity fluctuations and image quality fluctuations even during short-time processing. It relates to a photosensitive material.

[0007]

As a result of intensive studies, the present inventors have found that the object of the present invention can be achieved by the following, and have accomplished the present invention. That is, the present invention relates to a silver halide photographic light-sensitive material having on a support at least one silver halide emulsion layer containing light-sensitive silver halide grains chemically sensitized by a sulfur sensitizer and a gold sensitizer. In, the contribution of the sensitization by the sulfur sensitizer to the sensitivity of the silver halide emulsion layer does not eliminate the gold sensitizing effect when the sensitivity of the silver halide emulsion layer eliminates the effect of gold sensitization. The photosensitive silver halide grains are chemically sensitized so as to have a sensitivity of 20% to 80% in the state, and the photosensitive silver halide grains contain 90 mol% or more of silver chloride. And at least one heavy metal selected from the group VIII metals of the periodic table, the group II transition metals of the periodic table, lead, rhenium, molybdenum, tungsten and chromium inside and / or on the surface of the photosensitive silver halide grains. ion A silver halide photographic material which is a by which the photosensitive silver halide grains have.

The present invention will be described in more detail below.
The silver halide emulsion used in the silver halide photographic light-sensitive material according to the present invention is characterized by containing 90 mol% or more of silver chloride, and the content of silver chloride is more preferably 97 to 99.9 mol%. preferable. When the amount of development or the replenishment amount of the color developing solution is reduced in a shorter time, 99.5 to 99.
It is more preferably 9 mol%.

The photosensitive silver halide grains according to the present invention are
It may have a locally high silver bromide content.
Even if the portion containing silver bromide in a high concentration is epitaxially bonded to the silver halide emulsion grains, the so-called core
It may be a shell emulsion, or it may not form a complete layer but merely have regions having different compositions. The portion in which silver bromide is present at a high concentration may be formed in the step of forming silver halide grains, the chemical ripening step thereafter, or the coating solution preparation step. Further, when the composition of the inside of the particle is different from that of the surface, the composition may be changed continuously or discontinuously.

When the silver bromide content is about 1 mol%, the silver bromide content of the portion containing a high concentration of silver bromide depends on the composition of the entire photosensitive silver halide grain. 40 mol%
The above is preferable. Examples of such photosensitive silver halide grains include the grains described in JP-A-58-95736, JP-A-58-108533, and JP-A-1-183647.

The silver bromide content of the portion containing a high concentration of silver bromide can be determined by the method described in JP-A-1-183647, page 22, upper right column. When the silver bromide content thus obtained has a range, the silver bromide content of the portion containing silver bromide in a high concentration as referred to in this specification means the maximum value thereof.

The silver halide emulsion layer may contain substantially non-photosensitive silver halide grains. Therefore, the photosensitive silver halide grains used in the present invention are
It is preferably used in an amount of, for example, 20% by weight or more, more preferably 80% by weight or more. In the present invention, when it is described as silver halide grains, it means photosensitive silver halide grains.

When the silver halide emulsion according to the present invention contains a heavy metal ion, these compounds are useful for improving the reciprocity law failure, but the performance tends to change depending on the time from the exposure to the development. There are drawbacks. According to the present invention, this drawback can be improved and the advantage of improving reciprocity failure can be exhibited, which is a preferred embodiment of the present invention.

Heavy metal ions that can be used for such purposes include iron, iridium, platinum, palladium, nickel, rhodium, osmium, ruthenium, cobalt, and other metals of Group VIII of the periodic table, and cadmium.
Examples include periodic group II transition metals such as zinc and mercury, and ions of lead, rhenium, molybdenum, tungsten, and chromium. Among them, iron, iridium, platinum,
Ruthenium and osmium transition metal ions are preferred.

These heavy metal ions can be added to the silver halide emulsion in the form of salt or complex salt. Above all, it is preferable to add it in the form of a complex salt to the emulsion because it is easily incorporated into the silver halide emulsion and the effect of the present invention becomes large.

When the heavy metal ion forms a complex, examples of the ligand include cyanide ion, thiocyanate ion, cyanate ion, chloride ion, bromide ion, iodide ion, carbonyl, ammonia and the like. be able to. Among them, thiocyanate ion, isothiocyanate ion, cyanate ion and the like are preferable. The heavy metal compounds that can be preferably used in the silver halide emulsion according to the present invention are shown below, but the present invention is not limited thereto.

(1) FeCl ₂ (2) FeCl ₃ (3) (NH ₄ ) Fe (SO ₄ ) ₂ (4) K ₃ [Fe
(CN) ₆ ] (5) K ₄ [Fe (CN) ₆ ] (6) K ₂ [Ir
Cl ₆ ] (7) K ₃ [IrCl ₆ ] (8) K ₂ [Pt
Cl ₆ ] (9) K ₂ [Pt (SCN) ₄ ] (10) K ₂ [N
iCl ₄ ] (11) K ₂ [PdCl ₆ ] (12) K ₃ [P
dCl ₆ ] (13) CdCl ₂ (14) ZnCl
₂ (15) K ₂ [Mo (CO) ₄ (CNO) ₂ ] (16) K ₃ [Re (CNO) ₆ ] (17) K ₃ [Mo (CNO) ₆ ] (18) K ₄ [Fe (CNO] ) ₆ ] (19) K ₂ [W (CO) ₄ (CNO) ₂ ] (20) K ₂ [Cr (CO) ₄ (CNO) ₂ ] (21) K ₄ [Ru (CNO) ₆ ] (22) K ₂ [Ni (CN) _{4] (23) PbCl 2 (24)} K 3 [Co (NH _{3) 6]} (25) K ₅ [Co ₂ (CNO) _11] (26) K ₃ [Re (CNO) ₆ ] (27) K ₄ [Os (CNO) ₆ ] (28) K ₂ [Cd (CNO) ₄ ] (29) K ₂ [Pt (CNO) ₄ ] (30) K ₃ [IrBr ₆ ]

In order to add a heavy metal ion to the silver halide emulsion according to the present invention, the heavy metal compound is added to the physical layer before the formation of silver halide grains, during the formation of silver halide grains and after the formation of silver halide grains. It may be added at any place during each step during aging. For this purpose, for example, this heavy metal compound may be added as an aqueous solution at a desired timing. Alternatively, it may be dissolved together with the halide salt and added continuously during the grain formation process.

The amount of the heavy metal ions added to the silver halide emulsion is 1 × 10 ^-9 per mol of silver halide.
More preferably, it is 1 × 10 ⁻² mol or less, particularly 1 ×.
It is preferably 10 ^-8 mol or more and 1 × 10 ^-3 mol or less. The silver halide grains according to the present invention may have any shape, but a cubic having a (100) plane as a crystal surface or an area ratio of the (100) plane in the crystal surface is 14% or more. A face piece is preferred.

The production of the silver halide grain emulsion according to the present invention is described in JP-A-59-45437 and JP-A-55-2.
No. 6589, Japanese Patent Publication No. 55-42737, U.S. Pat. No. 41
No. 83756, No. 4225666, Journal
of Photographic Science
The method described in the literature such as Vol. 21, 39 (1973) can be referred to. The silver halide grain according to the present invention,
Particles having a single shape may be used, or particles having various shapes may be mixed.

The grain size of the silver halide grain according to the present invention is not particularly limited, but in view of other photographic properties such as rapid processing property and sensitivity, it is preferably 0.1 to 1.2 μm.
m, and more preferably 0.2 to 1.0 μm. The particle size can be measured by various methods commonly used in the technical field. As a typical method, Loveland's "particle size analysis method"
(ASTM Symposium on Right Microscopy, pp. 94-122, 1955), or "Theory of Photographic Process, 3rd Edition" (Co-authored by Mies and James, Chapter 2, published by Macmillan, Inc., 1966).

This particle size can be measured using the projected area of the particle or a diameter approximation. If the particles are of substantially uniform shape, the particle size distribution can be fairly accurately expressed as a diameter or projected area. The grain size distribution of the silver halide grains used in the present invention may be polydisperse or monodisperse. The monodisperse silver halide grains preferably have a coefficient of variation of 0.22 or less, more preferably 0.15 or less. Here, the coefficient of variation is a coefficient representing the breadth of the particle size distribution and is defined by the following equation.

Coefficient of variation = S / R (where S is the standard deviation of the grain size distribution and R is the average grain size.) The grain size referred to here is the diameter of spherical silver halide grains. Also, in the case of particles other than cubes and spheres, the diameter of the projected image converted into a circular image of the same area is shown.
As a device and method for preparing a silver halide emulsion, various devices and methods known in the art can be used.

The silver halide emulsion according to the present invention may be obtained by any of the acidic method, the neutral method and the ammonia method. The grains may be grown at one time, or may be grown after the seed grains are formed. The method for making seed particles and the method for growing seed particles may be the same or different.

The method of reacting the soluble silver salt and the soluble halide salt may be any of a forward mixing method, a back mixing method, a simultaneous mixing method, a combination thereof, etc., but the one obtained by the simultaneous mixing method. Is preferred. Further, the pAg controlled double jet method described in JP-A-54-48521 may be used as one form of the simultaneous mixing method.

In addition, JP-A-57-92523 and 57.
-92524, etc., a device for supplying an aqueous solution of a water-soluble silver salt and a water-soluble halide salt from an addition device arranged in a reaction mother liquor, a water-soluble silver salt and a water-soluble silver salt described in German Published Patent No. 292164, etc. Device for continuously changing the concentration of halide salt aqueous solution and adding it, Japanese Patent Publication No. 56-50
An apparatus for forming grains while keeping the distance between silver halide grains constant by taking out the reaction mother liquor from the reactor described in No. 1776 and concentrating it by ultrafiltration may be used.

Further, if necessary, a silver halide solvent such as thioether may be used. Further, a compound having a mercapto group, a nitrogen-containing heterocyclic compound or a compound such as a sensitizing dye may be added and used during the formation of silver halide grains or after the completion of grain formation.

The chemical sensitization of the silver halide emulsion according to the present invention is carried out by combining a sensitization method using a sulfur compound (sulfur sensitization) and a sensitization method using a gold compound (gold sensitization). As the sulfur sensitizer applicable in the present invention, 1,3-diphenylthiourea, triethylthiourea, 1-ethyl-3-
Preferred examples include thiourea derivatives such as (2-thiazolyl) thiourea, rhodanine derivatives, dithicarbamic acids, polysulfide organic compounds, sodium thiosulfate, sulfur simple substance and the like. As the simple substance of sulfur, α-sulfur belonging to the orthorhombic system is preferable.

Other sulfur sensitizers include US Pat. Nos. 1,574,944, 2,410,689, 2,278,947, 2,728,668 and 3,501. No. 313, No. 3,656,955, etc., West German application publication (OLS) 1,422,869
The sulfur sensitizers described in JP-A Nos. 56-24937 and 55-45016 can also be used. Examples of the gold sensitizer include chloroauric acid, gold thiosulfate, gold thiocyanate, and the like, as well as thioureas, rhodanines, and gold complexes of various compounds.

The amount of sulfur sensitizer and gold sensitizer used is not uniform depending on the type of silver halide emulsion, the type of compound used, ripening conditions, etc.
It is preferably 1 × 10 ⁻⁴ mol to 1 × 10 ⁻⁹ mol per mol. Further, preferably 1 × 10 ⁻⁵ mol to 1 × 1
It is ^0-8 mol. The sulfur sensitizer and gold sensitizer may be added by dissolving them in water or alcohols, other inorganic or organic solvents, and adding them in the form of a solution. A solvent insoluble in water or a medium such as gelatin. May be used in the form of a dispersion obtained by emulsifying and dispersing.

In the present invention, both sulfur sensitization and gold sensitization may be performed at the same time, or may be performed separately and stepwise. In the latter case, it is preferable to perform gold sensitization after or appropriately during sulfur sensitization. In the present invention, the contribution of the sensitizing effect by sulfur sensitization is evaluated by a sulfur sensitizer at a certain time under a certain aging (reaction) condition, as shown in Example 1 described later. And the sensitivity obtained by using the gold sensitizer in combination with the sensitivity obtained by using the sulfur sensitizer alone without adding the gold sensitizer under the same conditions (percentage based on the former). I will decide.

The definition (determination method) of the contribution ratio of sensitivity and sulfur sensitization is also described in Example 1. The conditions of the developing solution for determining the sensitivity are preferably those suitable for the original use and purpose of the photographic light-sensitive material of the present invention. The contribution of sulfur sensitization was evaluated by using a photographic light-sensitive material obtained by using a silver halide grain emulsion chemically sensitized in combination with sulfur sensitization and gold sensitization. E. Spencer
Method of Journal of Imaging Sc
Ience 32, 28-34 (1988), by comparing the sensitivity after removing the effect of gold sensitization by immersing in KCN solution and the sensitivity without removing the effect of gold sensitization. You can also In this case, the photographic light-sensitive materials themselves are advantageous in that the sensitivities can be compared.

In the chemical sensitization applied to the silver halide emulsion according to the present invention, the contribution ratio of sulfur sensitization determined by the above method is relative to the sensitivity obtained by the combined use of sulfur sensitization and gold sensitization. 20% or more and 80% or less. Furthermore, it is preferably in the range of 30% or more and 70% or less.

In the present invention, in order to make the contribution ratio of sulfur sensitization of 20 to 80%, the conditions for chemically sensitizing a silver halide emulsion, such as sulfur sensitizer, gold sensitizer and spectral sensitizer. The amount of the sensitizing dye, the chemical sensitizing dye auxiliary agent, etc., the addition time, temperature, reaction environmental conditions such as pAg and pH, etc. are controlled. The appropriate conditions for each of the variable factors depend on the shape, composition, quantity, etc. of the silver halide grains, so it cannot be said unequivocally, but the temperature is 40-80 ° C, pA
It is preferable that g is 5 to 9 and pH is 4 to 8.

The timing of applying the sulfur sensitizing dye and gold sensitization is
Even at the same time, sulfur sensitization may be performed first, and then gold sensitization may be performed during or after the sulfur sensitization. Moreover, the reverse order may be sufficient. Most preferably, the silver halide emulsion is optimally subjected to only sulfur sensitization and then gold sensitization is added so that the contribution of sulfur sensitization becomes a desired value. It is to change and adjust the amount of the sensitizer added and / or any of the above-mentioned other variable factors.

The silver halide emulsion according to the present invention can also be selenium sensitized. Examples of the selenium sensitizer include aliphatic isoselenocyanates such as allyl isoselenocyanate, selenoureas, selenoketones, selenoamides, selenocarboxylic acids, selenoesters, selenophosphates, diethyl selenide, and diethyl diselena. Examples include selenides such as id. Specific examples thereof and other compounds and specific examples of use techniques are disclosed in the following patent specifications or patent publications.

US Pat. Nos. 1,574,944, 1,602,592, 1,623,499, 3,297,446, 3,297,447,
No. 3,320,069, No. 3,408,196
No. 3,408,197, No. 3,442,65
No. 3, No. 3,420,670, No. 3,591,3
No. 85, French Patent Nos. 2,693,038 and 2,
093,209, Japanese Examined Patent Publication No. 52-34491, 52
-34492, 53-295, and 57-2209.
No. 0, JP-A-59-180536 and JP-A-59-1853.
30, No. 59-181337, No. 59-18733.
No. 8, No. 59-192241, No. 60-150046.
No. 60-151637 and No. 61-246738.
No. 3, Unexamined Japanese Patent Publication No. 3-4221, No. 3-24537, No. 3
-111838, 3-116132, 3-14
8648, 4-16838, 4-96059
No. 4-109240, 4-140738, 4-140739, 4-147250, 4-1.
49437, British Patents 255,846 and 861,
984, and H.M. E. Journal by Spencer et al.
al of Photographic Science
e magazine, Vol. 31, pp. 158-169 (1983).

The silver halide emulsion according to the present invention can be reduction-sensitized by a known method. For example, it is possible to use a method of adding various reducing agents, a method of aging under conditions of high silver ion concentration, or a method of aging under conditions of high pH.

As the reducing agent used for reduction sensitization of the silver halide emulsion according to the present invention, stannous salts such as stannous chloride, boranes such as tri-t-butylamineborane, sodium sulfite, potassium sulfite, etc. Examples thereof include sulfites, reductones such as ascorbic acid, and thiourea dioxide. Among these, thiourea dioxide, ascorbic acid and its derivatives, and sulfite can be preferably used. Compared with the case where reduction sensitization is performed by controlling the silver ion concentration and pH during ripening, the method using a reducing agent as described above has excellent reproducibility and is preferable.

These reducing agents are dissolved in a solvent such as water or alcohol and added to the silver halide emulsion for ripening, or they are added during ripening of the silver halide grains to reduce and increase them simultaneously with grain formation. You may feel. The amount of these reducing agents to be added needs to be adjusted according to the pH of the silver halide emulsion, the concentration of silver ions, etc., but generally 10 ^-7 to 10 ^-2 mol per mol of the silver halide emulsion. preferable.

After the reduction sensitization, a small amount of an oxidizing agent may be used in order to modify the reduction sensitizing nucleus or deactivate the remaining reducing agent. Examples of the compound used for such purpose include
Examples thereof include potassium hexacyanoferrate (III), bromosuccinimide, p-quinone, potassium perchlorate, and hydrogen peroxide solution.

The silver halide emulsion according to the present invention is intended to prevent fog that occurs during the process of preparing a silver halide photographic light-sensitive material, reduce performance fluctuation during storage, and prevent fog that occurs during development. Known antifoggants and stabilizers can be used. Examples of compounds that can be used for such purpose include compounds represented by the general formula (II) described in JP-A-2-146036, page 7, column, and specific examples thereof include:
(IIa-1) to (IIa-) described on page 8 of the publication.
8), compounds of (IIb-1) to (IIb-7), and
Examples thereof include 1- (3-methoxyphenyl) -5-mercaptotetrazole.

These compounds are added in the steps such as the step of preparing silver halide emulsion grains, the step of chemical sensitization, the end of the chemical sensitization step and the step of preparing a coating solution, depending on the purpose. When chemical sensitization is carried out in the presence of these compounds, 1 × 10 ⁻⁵ mol to 5 × 10 ⁵ mol per mol of silver halide.
It is preferably used in an amount of about ^-4 mol. When added at the end of chemical sensitization, 1 × 10 1 per mol of silver halide
^-6 mol to ^{1x10 -2} mol is preferable, and 10x5 is preferable.
^-5 mol to 5 x 10 ^-3 mol is more preferable.

When added to the silver halide emulsion layer in the coating solution preparation step, 1 × per mol of silver halide.
An amount of about 10 ⁻⁶ to 1 × 10 ⁻¹ mol is preferable, and 1 × 10 1.
More preferably, it is ^-5 mol to 1 x 10 ^-2 mol. When it is added to a layer other than the silver halide emulsion layer, the amount in the coating film is preferably about 1 × 10 ⁻⁹ mol to 1 × 10 ⁻³ mol.

When the silver halide photographic light-sensitive material according to the present invention is used as a color photographic light-sensitive material, it is spectrally sensitized to a specific region in the wavelength range of 400 to 900 nm by combining it with a yellow coupler, a magenta coupler and a cyan coupler. It has a layer containing a silver halide emulsion. The silver halide emulsion contains one kind or a combination of two or more kinds of sensitizing dyes.

Any known compound can be used as the spectral sensitizing dye used in the silver halide emulsion according to the present invention, and as the blue-sensitive sensitizing dye, Japanese Patent Application No.
BS-1 to BS-8 described in JP-A-51124 (see JP-A-3-251840), pages 108 to 109 can be preferably used alone or in combination. As the green sensitizing dye, GS-1 to 5 described on page 110 of the same specification are preferably used. As the red-sensitizing sensitizing dye, R described in pages 111 to 112 of the same specification is used.
S-1 to S-8 are preferably used.

When the silver halide photographic light-sensitive material according to the present invention is exposed by a printer using a semiconductor laser, it is necessary to use a sensitizing dye having infrared sensitivity, which is an infrared-sensitive sensitizing dye. As for Japanese Patent Application No. 3-7361
9 IRS-1 to 11 described on pages 12 to 14 of the same specification
The above dyes are preferably used. In addition, the same specification 14 to 1
The supersensitizers SS-1 to SS-9 described on page 5 are preferably used in combination with these dyes.

When the silver halide photographic light-sensitive material according to the present invention is exposed using a laser, it is advantageous to use an exposure device using a semiconductor laser in terms of downsizing of the device. In scanning exposure, the exposure time per pixel corresponds to the exposure time actually received by the silver halide emulsion, but the exposure time per pixel is the luminous flux in the case of scanning exposure with laser light. In the spatial change of the intensity of the light, the outer edge of the light flux is defined as the point where the light intensity becomes 1/2 of the maximum value, and the outer edge of the light flux and the line that is parallel to the scanning line and that passes through the point where the light intensity is the maximum. When the distance between two intersecting points is the diameter of the light beam, the (light beam diameter) / (scanning speed) can be considered as the exposure time per pixel. As the exposure time per pixel becomes shorter, the relationship between the exposure time and the color density tends to become more complicated, and the present invention is particularly effective when an apparatus having a short exposure time per pixel is used.

A laser printer device that is considered to be applicable to such a system is, for example, Japanese Patent Laid-Open No.
-4071, JP-A-59-11062, JP-A-63.
-197947, JP-A-2-74942, JP-A-2
-236538, Japanese Examined Patent Publication No. 56-14963, Japanese Examined Patent Publication No. 56-40822, European Wide Area Patent 77410, Electronic Communication Department Technical Report 80 Vol. 244, and Movie Television Technical Journal 1984/6 (382), 34-. Some are described on page 36.

In the silver halide photographic light-sensitive material according to the present invention, dyes having absorption in various wavelength regions can be used for the purpose of preventing irradiation and halation. For this purpose, any known compound can be used, but in particular, as a dye having absorption in the visible region,
The dyes of AI-1 to 11 described in Japanese Patent Application No. 2-51124, pages 117 to 118 are preferably used, and as infrared absorbing dyes, general dyes described in JP-A 1-280750, page 2, lower left column. Formulas (I), (II), (I
The compound represented by II) has preferable spectral characteristics and is preferable because it does not affect the photographic characteristics of the silver halide photographic emulsion and does not cause contamination due to residual color. Specific examples of preferable compounds include Exemplified Compounds (1) to (45) listed on page 3, lower left column to page 5, lower left column.

As the coupler used in the silver halide photographic light-sensitive material according to the present invention, a coupling product having a spectral absorption maximum wavelength in a wavelength range longer than 340 nm is formed by a coupling reaction with an oxidant of a color developing agent. Any compound that can be used can be used, but as a particularly representative example, a yellow coupler having a spectral absorption maximum wavelength in a wavelength range of 350 to 500 nm, a wavelength range of 500 to 60
A magenta coupler having a spectral absorption maximum wavelength at 0 nm,
A known one is a cyan coupler having a spectral absorption maximum wavelength in a wavelength range of 600 to 750 nm.

A yellow coupler which can be preferably used in the silver halide photographic light-sensitive material according to the present invention is described in Japanese Patent Application No. 2-234208 (JP-A-4-11).
No. 4154), and couplers represented by the general formula (YI) described on page 8 can be mentioned. Specific compounds include those described as YC-1 to YC-9 on pages 9 to 11 of the same specification. Among them, YC-8 and YC-9 described on page 11 of the same specification are preferable because they can reproduce a preferable yellow color.

As the magenta coupler which can be preferably used in the silver halide photographic light-sensitive material of the present invention, the general formula (M-I) and the general formula (M) described on page 12 of Japanese Patent Application No. 2-234208. A coupler represented by -II) may be mentioned. Specific compounds include those described as MC-1 to MC-11 on pages 13 to 16 of the same specification. Above all, the same specification 1
MC-8 to MC-11 described on pages 5 to 16 are preferable because they are excellent in the reproduction of colors from blue to purple and red, and are also excellent in the depiction of details.

Cyan couplers that can be preferably used in the silver halide photographic light-sensitive material of the present invention include:
Examples thereof include couplers represented by the general formula (CI) and the general formula (C-II) described on page 17 of Japanese Patent Application No. 4-114154. Specific compounds are described in the same specification 1
Examples thereof include those described as CC-1 to CC-9 on pages 8 to 21.

In the case of the oil-in-water type emulsion dispersion method used to add the coupler used in the silver halide photographic light-sensitive material of the present invention, it is usually used in a water-insoluble high-boiling point organic solvent having a boiling point of 150 ° C. or higher. If necessary, a low-boiling point and / or water-soluble organic solvent is also used in combination to dissolve, and a surfactant is emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution.

As a dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser or the like can be used. After the dispersion or at the same time as the dispersion, a step of removing the low boiling point organic solvent may be added.
As the high boiling point organic solvent that can be used for dissolving and dispersing the coupler, phthalic acid esters such as dioctyl phthalate and phosphoric acid esters such as tricresyl phosphate are preferably used.

In place of the method using a high-boiling point organic solvent, the coupler and a water-insoluble and organic solvent-soluble polymer compound are dissolved in a low-boiling point and / or water-soluble organic solvent, if necessary, to prepare a gelatin aqueous solution or the like. It is also possible to employ a method of emulsifying and dispersing by using various dispersing means using a surfactant in a hydrophilic binder. The water-insoluble organic solvent-soluble polymer used at this time is poly (Nt
-Butylacrylamide) and the like.

For the purpose of shifting the absorption wavelength of the color forming dye, the compound (d-11) described on page 33 of Japanese Patent Application No. 2-234208 and the compound (A'-1) described on page 35 of the specification. And other compounds can be used. Also,
Besides, the fluorescent dye-releasing compounds described in US Pat. No. 4,774,187 can also be used.

The coating amount of the coupler is not particularly limited as long as a sufficiently high concentration can be obtained, but it is preferably 1 × 10 ^{−3 to} 5 mol, and more preferably 1 mol per mol of silver halide. It is used in a range of × 10 ^-2 to 1 mol.

In the silver halide photographic light-sensitive material of the present invention, it is advantageous to use gelatin as a binder, but if necessary, other gelatin, gelatin derivatives, graft polymers of gelatin and other polymers, gelatin. Other than the above, hydrophilic colloids such as proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as single or copolymers can also be used.

As the reflective support according to the present invention, any material may be used, including white pigment-containing polyethylene-coated paper, baryta paper, vinyl chloride sheet, white pigment-containing polypropylene, polyethylene terephthalate support and the like. Can be used. Above all, a support having a polyolefin resin layer containing a white pigment on its surface is preferable.

As the white pigment used in the reflective support according to the present invention, inorganic and / or organic white pigments can be used, and preferably inorganic white pigments are used. For example, alkaline earth metal sulfates such as barium sulfate, alkaline earth metal carbonates such as calcium carbonate, finely divided silicic acid, silicas such as synthetic silicates, calcium silicate, alumina, alumina hydrate, oxidation Examples thereof include titanium, zinc oxide, talc, clay and the like. The white pigment is preferably barium sulfate or titanium oxide.

The amount of the white pigment contained in the waterproof resin layer on the surface of the reflective support according to the present invention is preferably 10% by weight or more as the content in the waterproof resin layer,
Further, the content is preferably 13% by weight or more, and more preferably 15% by weight or more.

The dispersity of the white pigment in the water resistant resin layer of the paper support according to the present invention can be measured by the method described in JP-A-2-28640. When measured by this method, the degree of dispersion of the white pigment is preferably 0.20 or less, more preferably 0.15 or less, and 0.10 or less as the coefficient of variation described in the above publication. Is more preferable.

In the silver halide photographic light-sensitive material according to the present invention, the support surface is subjected to corona discharge, ultraviolet irradiation, flame treatment, etc., if necessary, and then directly or undercoat layer (adhesiveness of the support surface, Applied through one or more undercoat layers for improving antistatic properties, dimensional stability, abrasion resistance, hardness, antihalation properties, friction properties and / or other properties) Good.

In coating a photographic light-sensitive material using a silver halide emulsion, a thickener may be used to improve coatability. As the coating method, extrusion coating and curtain coating which can simultaneously coat two or more layers are particularly useful.

As the aromatic primary amine developing agent used in the present invention, known compounds can be used. The following compounds can be mentioned as an example of these compounds.

CD-1) N, N-diethyl-p-phenylenediamine CD-2) 2-amino-5-diethylaminotoluene CD-3) 2-amino-5- (N-ethyl-N-laurylamino) toluene CD-4) 4- (N-ethyl-N- (β-hydroxyethyl) amino) aniline CD-5) 2-methyl-4- (N-ethyl-N- (β-
Hydroxyethyl) amino) aniline CD-6) 4-amino-3-methyl-N- (β- (methanesulfonamido) ethyl) -aniline CD-7) N- (2-amino-5-diethylaminophenylethyl) methane Sulfonamide CD-8) N, N-dimethyl-p-phenylenediamine CD-9) 4-amino-3-methyl-N-ethyl-N-
Methoxyethylaniline CD-10) 4-amino-3-methyl-N-ethyl-N
-(Β-Ethoxyethyl) aniline CD-11) 4-amino-3-methyl-N-ethyl-N
-(Β-Butoxyethyl) aniline

In the case of the image forming method used in the present invention, the compound represented by the following formula (CD-1) is more preferably used from the viewpoint of developing treatment for a short time.

[0070]

[Chemical 1]

In the formula (CD-1), R is a linear or branched alkylene group having 3 carbon atoms, and m and n are each 1
Is an integer of ~ 4, HA represents an inorganic or organic acid,
For example, it represents hydrochloric acid, sulfuric acid, nitric acid, p-toluenesulfonic acid, or the like. These color developing agents are
American Chemical Society Volume 73, 3100
It can be easily synthesized by the method described in (1951). Specific examples of the compound represented by formula (CD-1) are shown below.

[0072]

[Chemical 2]

[0073]

[Chemical 3]

The color-developing agent according to the present invention is usually used in the range of 1 × 10 ^-2 to 2 × 10 ^-1 mol per liter of developing solution, and from the viewpoint of rapid processing, it is 1 per liter of color developing solution. It is preferably used in the range of 0.5 × 10 ^{-2 to} 2 × 10 ^-1 mol. The color developing agent used in the image forming method of the present invention may be used alone or in combination with other known p-phenylenediamine derivatives.

In the image forming method of the present invention, (CD-5), (CD-6) and (CD-9) are preferable as the compound used in combination with the compound represented by the general formula [A]. These p-phenylenediamine derivatives are
It is generally used in the form of salt such as sulfate, hydrochloride, sulfite, nitrate and p-toluenesulfonate.

The color developer according to the present invention may contain the following developer components in addition to the above components. As the alkaline agent, for example, sodium hydroxide, potassium hydroxide, sodium metaborate, potassium metaborate, trisodium phosphate, tripotassium phosphate, borax, silicates, etc. may be used alone or in combination to prevent precipitation. , P
It can be used in combination within a range that maintains the H stabilizing effect. Further, disodium hydrogen phosphate, for the purpose of preparation or for the purpose of increasing ionic strength,
Various salts such as dipotassium hydrogen phosphate, sodium bicarbonate, potassium bicarbonate and borate can be used.

If necessary, inorganic and organic antifoggants can be added. For the purpose of suppressing development, halide salt ions are often used,
When an image is formed using the silver halide photographic light-sensitive material of the present invention, it is necessary to finish development in a very short time, so chloride ions are mainly used, and potassium chloride, sodium chloride, etc. are used. . The amount of chloride ion is about 3.0 × 10 ^-2 mol or more, preferably 4.0 × 10 ^{-2 to} 5.0 × 10 ^-1 mol per liter of the color developing solution. Bromide ions can be used within a range that does not impair the effects of the present invention, but have a large effect of suppressing development, and are approximately 1.0 × 1 per liter of color developing solution.
It is desirable that the amount is 0 ^-3 mol or less, preferably 5.0 × 10 ^-4 or less.

Furthermore, if necessary, a development accelerator can be used. Examples of the development accelerator include various pyridinium compounds represented by U.S. Pat. Nos. 2,648,604, 3,671,247 and JP-B-44-9503, other cationic compounds, and phenosafranine. Cationic dyes, neutral salts such as thallium nitrate, US Pat. Nos. 2,533,990 and 2,531,8
No. 32, No. 2,950,970, No. 2,577,12
Nonionic compounds such as polyethylene glycol and its derivatives, and polythioethers described in JP-B No. 7-944 and JP-B-44-9504, organic solvents, organic amines, ethanolamine, ethylenediamine, diethanolamine, triethanol described in JP-B-44-9509. Includes amines and the like.

Further, phenethyl alcohol described in US Pat. No. 2,304,925 and other acetylene glycol, methyl ethyl ketone, cyclohexanone,
Pyridine, ammonia, hydrazine, thioethers,
Examples thereof include amines. Further, in the color developer according to the present invention, if necessary, ethylene glycol, methyl cellosolve, methanol, acetone, dimethylformamide, β-cyclodextrin, and other Japanese Patent Publication No. 47-3.
The compounds described in Japanese Patent Nos. 3378 and 44-9509 can be used as an organic solvent for increasing the solubility of the developing agent.

Further, an auxiliary developing agent can be used together with the developing agent. Examples of these auxiliary developers include N-methyl-p-aminephenol sulfate, phenidone, N, N'-diethyl-p-aminophenol hydrochloride, N, N, N ', N'-tetramethyl- P-phenylenediamine hydrochloride and the like are known, and the addition amount thereof is usually 0.01 to 1.0 g per liter of the developing solution.
Used. In addition to these, competing couplers, fogging agents, development inhibitor-releasing couplers (so-called DIR couplers), development inhibitor-releasing compounds and the like can be added as required.

Furthermore, various additives such as other stain preventing agents, sludge preventing agents and multi-layer effect accelerators can be used. Each component of the above color developing solution can be prepared by sequentially adding and stirring to a fixed amount of water. In this case, the component having low solubility in water can be added by mixing with the above-mentioned organic solvent such as triethanolamine. Further, more generally, a color developing solution according to the present invention is prepared by adding a plurality of components, each of which can coexist in a stable manner, in a concentrated aqueous solution, or by adding in a solid state a small container prepared in advance in water and stirring. Can also be prepared.

In the present invention, the above-mentioned color developing solution can be used in an arbitrary pH range, but from the viewpoint of rapid processing, the pH is not higher than 9.
It is preferably 5 to 13.0, and more preferably used in a pH range of 9.8 to 12.0. The processing temperature for color development according to the present invention is preferably 35 ° C. or higher and 70 ° C. A higher temperature is preferable because the treatment can be performed for a shorter time, but it is preferably not so high in view of the stability of the treatment liquid, and the treatment is preferably performed at 37 ° C or higher and 60 ° C or lower.

Conventionally, the color development time is generally about 3 minutes and 30 seconds, but in the present invention, it is within 25 seconds.
Further, it is preferable to carry out in the range of 20 seconds to 3 seconds. The processing steps substantially consist of a color developing step, a bleach-fixing step, and a washing step (including a stabilizing treatment as an alternative to washing with water), but steps may be added or have equivalent meanings within a range that does not impair the effects of the present invention. Can be replaced with For example, the bleach-fixing step can be separated into a bleaching step and a fixing step, or the bleaching step can be performed before the bleach-fixing step. The processing steps used in the image forming method of the present invention include:
It is preferable to provide a bleach-fixing step immediately after the color developing step.

The bleaching agent that can be used in the bleach-fixing solution used in the image forming method of the present invention is not limited, but is preferably a metal complex salt of an organic acid. The complex salt is obtained by coordinating an organic acid such as polycarboxylic acid, aminopolycarboxylic acid or oxalic acid or citric acid with a metal ion such as iron, cobalt or copper. The most preferred organic acid used to form such a metal complex salt of an organic acid includes
Mention may be made of polycarboxylic acids or aminopolycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.

Specific examples of these compounds are described in JP-A-1
Compounds [2] to [20] described in JP-A-205262, pages 58 to 59 can be mentioned. These bleaching agents are used in an amount of 5-450 g, preferably 20-250 g, per liter of the bleach-fixing solution. As the bleach-fixing solution, a solution having a composition containing a silver halide fixing agent in addition to the above-mentioned bleaching agent and, if necessary, a sulfite as a preservative is applied.

Also, iron (III) ethylenediaminetetraacetate
A bleach-fixing solution having a composition in which a large amount of a halide such as ammonium bromide is added in addition to the acid bleaching agent and the silver halide fixing agent, and further ethylenediaminetetraacetic acid iron
II) A special bleach-fixing solution having a composition comprising a combination of an acid bleaching agent and a large amount of a halide such as ammonium can be used. As the halide,
In addition to ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide and the like can be used.

The silver halide fixing agent contained in the bleach-fixing solution is a compound which reacts with silver halide to form a water-soluble complex salt, such as potassium thiosulfate or sodium thiosulfate, which is used in ordinary fixing processing. Typical examples thereof include thiosulfates such as ammonium thiosulfate, potassium thiocyanate, sodium thiocyanate, thiocyanates such as ammonium thiocyanate, thiourea and thioether. These fixing agents are used in an amount of 5 g or more per liter of the bleach-fixing solution in a range where they can be dissolved, but generally 70 to 250 g.

The bleach-fix solution contains boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide and the like.
The buffer may be contained alone or in combination of two or more kinds. Furthermore, various fluorescent whitening agents, antifoaming agents or surfactants may be contained.

Further, hydroxylamine, hydrazine,
Preservatives such as bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids or stabilizers such as nitro alcohols and nitrates, and organic solvents such as methanol, dimethyl sulfonamide, dimethyl sulfoxide, etc. You can

The bleach-fixing solution according to the present invention is described in JP-A-46 / 46
-280, Japanese Patent Publication No. 45-8506, 46-556.
No., Belgian Patent 770910, Japanese Patent Publication No. 45-883
Various bleaching accelerators described in JP-A No. 6-53, JP-A-53-9854, JP-A-54-71634 and JP-A-49-42349 can be added.

The bleach-fix solution is used at a pH of 4.0 or higher, but is generally used at a pH range of 4.0 to 9.5.
It is preferably used at pH 4.5 to 8.5. Most preferably, it is used in the pH range of 5.0 to 8.5. The treatment is performed at a temperature of 80 ° C. or lower, preferably 55 ° C. or lower to prevent evaporation and the like. The processing time for bleach-fixing is preferably 3 to 45 seconds, more preferably 5 to 30 seconds.

In the developing treatment according to the present invention, washing with water is carried out subsequent to the color developing and bleach-fixing steps. A preferred embodiment of the washing treatment will be described below. As a compound preferably used in the washing solution, a chelating agent having a chelate stabilization constant for iron ions of 8 or more is preferable.

Here, the chelate stabilization constant is defined as L. G.
Sillen, A .; E. Martell, "Stab
ility Constants of Metali
on Complexes ", The Chemical
Society, London (1964) and S.S. C
haberek, A .; E. Martell, "Org
anic Sequestering Agent
s ”, Wiley (1959), etc., and generally known constants.

Examples of the chelating agent having a chelate stability constant of 8 or more for iron ions, which is preferably used in the washing solution, include organic carboxylic acid chelating agents, organic phosphoric acid chelating agents, inorganic phosphoric acid chelating agents, and polyhydroxy compounds. To be The iron ion means ferric ion.

The chelate stability constant with ferric ion is 8
Specific examples of the chelating agent as described above include compounds described in JP-A-1-205162, page 63, line 15 to page 64, line 17. The amount of the chelating agent used is preferably 0.01 to 50 g, and more preferably 0.05 to 20 g, per liter of the washing solution.

Further, as a compound added to the washing solution, an ammonium compound is mentioned as a particularly preferable compound. These are supplied by ammonium salts of various inorganic compounds, and specific examples thereof include compounds described in JP-A-1-205162, page 65, line 5 to page 66, line 11. The addition amount of the ammonium compound is preferably 1.0 × 10 ⁻⁵ mol or more, more preferably 0.001 to 5.0 mol, and further preferably 0.002 to 1.0 mol, per liter of the washing liquid. It is in the molar range.

Further, it is desirable that the washing liquid contains sulfite in an amount within the range where bacteria are not generated.
The sulfite contained in the washing solution may be any one such as an organic substance or an inorganic substance as long as it releases a sulfite ion, but is preferably an inorganic salt, and preferable specific compounds include sodium sulfite, potassium sulfite and ammonium sulfite. , Ammonium bisulfite, potassium bisulfite,
Examples thereof include sodium bisulfite, sodium metabisulfite, potassium metabisulfite, ammonium metabisulfite and hydrosulfite, cartaraldehyde bis sodium bisulfite, and succinic aldehyde bis sodium bisulfite.

It is preferable that at least 1.0 × 10 ^-5 mol of the sulfite is added to 1 liter of the washing solution,
More preferably, it is 5 × 10 ^{−5 to} 1.0 × 10 ⁻¹ mol. It may be added directly to the washing solution, but it is preferably added to the washing replenisher. The washing solution used in the present invention preferably contains a fungicide,
This makes it possible to prevent sulfidation and improve image storability.

Examples of the mildew-proofing agent that can be used in the washing solution according to the present invention include sorbic acid, benzoic acid compounds, phenol compounds, thiazole compounds, pyridine compounds, guadinine compounds, morpholine compounds, and quaternary compounds. Phosphonium compounds, ammonium compounds, urea compounds, isoxazole compounds, propanolamine compounds, sulfamide compounds, pyronone compounds and amino compounds.

Specific compounds are described in JP-A 1-20
Compounds described in JP-A No. 5162, page 68, line 10 to page 72, line 16 can be mentioned. Among these compounds, thiazole compounds, sulfamide compounds, and pyronone compounds are particularly preferably used. The amount of the antifungal agent added to the washing liquid is 0.001 to 1 liter of the washing liquid.
It is preferably used in the range of 30 g, and more preferably in the range of 0.003 to 5 g.

The washing liquid according to the present invention preferably contains a metal compound in combination with a chelating agent. Examples of such metal compounds include Ba, Ca, Ce, Co, In and L.
a, Mn, Ni, Bi, Pb, Sn, Ti, Zr, M
Examples thereof include compounds of g, Al and Sr. These metal compounds can be supplied as an inorganic or organic salt such as a halide salt, a sulfate salt, a carbonate salt, a phosphate salt or an acetate salt, a hydroxide or a water-soluble chelate compound. The addition amount of these compounds is 1.0 × 10 1 liter of the washing liquid.
^{-4 to} 1.0 x 10 ^-1 mol is preferable and 4.0 x 10 ^-4 to
2.0 × 10 ^-2 mol is more preferable.

In addition to the above, a compound having an aldehyde group may be used as the one contained in the washing solution according to the present invention. Specific compounds include, for example, JP-A-1-20516.
The Exemplified Compound 1 to Exemplified Compound 32 described on pages 73 to 75 of Japanese Patent Publication No. 2 can be mentioned. The compound having an aldehyde group is 0.1 to 50 g per 1 liter of washing water.
It is preferable to use in the range of 0.5 to 10 g.
It is preferably used in the range of.

Ion-exchanged water treated with an ion-exchange resin may be used as the washing solution according to the present invention. The pH of the washing solution applicable to the present invention is in the range of 5.5 to 10.0. As the pH adjuster applicable to the present invention, any of generally known alkali agents and acid agents can be used.

The treatment temperature of the water washing treatment is preferably 15 ° C to 60 ° C, more preferably 20 ° C to 45 ° C. Also,
The washing treatment time is preferably 5 to 60 seconds, more preferably 5 to 50 seconds. When the water washing treatment is performed in a plurality of tanks, it is preferable that the earlier tank is treated in a shorter time and the latter tank is treated in a longer time. The processing time of the back tank is 20 times that of the front tank.
It is preferable that the treatments are sequentially performed with the treatment time increasing by 50% to 50%.

In the case of the multi-tank counter flow current system, the method of supplying the washing solution in the washing step according to the present invention is preferably such that the washing solution is supplied to the post-bath and allowed to overflow into the pre-bath. Of course, it can also be processed in a single tank. As a method of adding the compound, various methods such as adding as a concentrated solution to the washing tank, or adding the above compound and other additives to the washing solution supplied to the washing tank, and using this as a washing replenisher Is used.

The amount of washing water in the washing step according to the present invention is preferably 0.1 to 50 times, and particularly preferably 0.5 to 30 times the carrying amount of the pre-bath (usually bleach-fixing solution or fixing solution) per unit area of the light-sensitive material. preferable. The washing tank in the washing treatment according to the present invention is preferably 1 to 5 tanks, and more preferably 1 to 3 tanks.

As a developing processing apparatus for the silver halide photographic light-sensitive material of the present invention, any known apparatus may be used. Specifically, it may be a roller transport type in which the photosensitive material is conveyed by sandwiching it between rollers arranged in a processing tank, or an endless belt method in which the photosensitive material is fixed to a belt and conveyed. A method of forming a processing tank in the shape of a slit and supplying the processing liquid to the processing tank while conveying the photosensitive material, a spray method of spraying the processing liquid, and a web method of contacting a carrier impregnated with the processing liquid. A method using a viscous treatment liquid can also be used.

When the silver halide photographic light-sensitive material of the present invention is used, the time from exposure to development may be any time, but a shorter time is preferred for shortening the entire processing time. preferable. Further, the silver halide photographic light-sensitive material according to the present invention is advantageous because the change in image density is small even when the time from exposure to development is 30 seconds or less and a high quality image can be stably obtained. Can be used for.

[0109]

EXAMPLES The present invention will be described below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 (Preparation of Blue-Sensitive Silver Halide Emulsion) 2 kept at 40 ° C.
% Gelatin aqueous solution 1000 ml
(Solution) and (solution B) are added simultaneously over 30 minutes while controlling pAg = 6.5 and pH = 3.0, and further (C)
Liquid) and (D liquid) were simultaneously added over 180 minutes while controlling pAg = 7.3 and pH = 5.5. PH at this time
Was controlled by the method described in JP-A-59-456437, and the pH was controlled by using an aqueous solution of sulfuric acid or sodium hydroxide.

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.03 g Water was added to 200 ml (Solution B) Silver nitrate 10 g Water was added to 200 ml (Solution C) Sodium chloride 102.7 g Potassium bromide 1. 0 g Potassium hexachloroiridium (IV) [Exemplified compound (6)] 20 × 10 ^-7 mol Water added 600 ml (D liquid) Silver nitrate 300 g Water added 600 ml

After the addition is completed, Demol N manufactured by Kao Atlas Co., Ltd.
Of 5% aqueous solution of magnesium sulfate and 20% aqueous solution of magnesium sulfate, and then mixed with an aqueous solution of gelatin to have an average particle size of 0.85 μm, coefficient of variation (S / R) = 0.07, silver chloride content. 99.5 mol% monodisperse cubic emulsion EMP-1
Got The above emulsion EMP-1 was divided into equal portions, and each of them was subjected to chemical sensitization by the following 9 types of prescriptions to obtain silver halide emulsions EM-B _{1 to} EM-B ₁₂ .

<Formulation-1> 4 × 10 ⁻⁴ mol of the sensitizing dye BS-1, 1 × 10 ⁻¹ mol of the sensitizing dye BS-2, and 6 parts of the stabilizer STAB-1 per mol of the silver halide. × 10 ^-4 mol, added in this order, and 5 minutes after that, sodium thiosulfate was added ⁴ times.
× 10 ^-6 mol, and 1 minute later, add 7 × 10 of chloroauric acid.
^-6 mol was added, and sodium thiosulfate was added at 60 ° C., followed by chemical aging for 120 minutes.

<Formulation-2> In Formulation-1, chemical aging was performed under the same conditions except that the addition timing of chloroauric acid was delayed. <Formulation-3> In Formulation-1, chemical aging was performed under the same conditions except that chloroauric acid was removed.

<Formulation-4> In Formulation-1, chemical ripening was performed under the same conditions except that triethylthiourea was used in place of sodium thiosulfate in an amount of 1 × 10 ⁻⁶ mol per mol of silver halide. . <Formulation-5> In Formulation-2, instead of sodium thiosulfate, triethylthiourea was used in an amount of 1 × 10 ⁻⁶ mol per mol of silver halide, and chloroauric acid was 2 × 10 ^−6.
Chemical aging was performed under the same conditions except that the mole was used.

<Formulation-6> In Formulation-4, chemical aging was performed under the same conditions except that chloroauric acid was removed. <Formulation-7> In Formulation-1, instead of sodium thiosulfate, 1, Chemical ripening was carried out under the same conditions except that 3-diphenylthiourea was used at 1 × 10 ⁻⁶ mol per mol of silver halide.

<Formulation-8> In Formulation-2, 1,3-diphenylthiourea was used in place of sodium thiosulfate in an amount of 1 × 10 ⁻⁶ mol per mol of silver halide, and chloroauric acid was 2 ×. Chemical aging was performed under the same conditions except that 10 ^-6 mol was used. <Formulation-9> In Formulation-7, chemical aging was performed under the same conditions except that chloroauric acid was removed.

<Formulation-10> In Preparation-1, chemical ripening was carried out under the same conditions except that, in place of sodium thiosulfate, simple substance of sulfur was used in an amount of 0.2 mg per mol of silver halide. <Formulation-11> In Formulation-2, simple substance of sulfur was replaced by 0.2 per mol of silver halide instead of sodium thiosulfate.
Chemical aging was performed under the same conditions except that 1 mg of chloroauric acid and 1 × 10 ⁻⁶ mol of chloroauric acid were used. <Formulation-12> In Formulation-10, chemical aging was performed under the same conditions except that chloroauric acid was removed.

After completion of the chemical ripening, stabilizer STA was added to each.
B-2 was added in an amount of 1 × 10 ⁻⁴ mol per mol of silver halide, and further 0.4 mol of yellow coupler Y-1 dissolved in dioctyl phthalate was added per mol of silver halide and dodecylbenzenesulfone as a coating aid. After the addition of sodium acid, it was coated on a paper support coated with titanium oxide-containing polyethylene so that the coated silver amount was 0.35 g / m ² and gelatin was 3.0 g / m ² . Further thereon, 4.0 g / m ² of gelatin was applied as a protective layer.

The sample No. prepared as described above. 1 to
No. 12 sheets of 3 sheets each were prepared, and a KS-7 type sensitometer (manufactured by Konica Corporation) was used to perform wedge exposure for 0.5 second, then 1 sheet was exposed for 1 minute and 1 sheet was exposed. 5 minutes later,
The remaining 1 sheet is 10 minutes after the exposure and the following development processing step (A) is performed.
The development and fixing processes were carried out according to the above. After completion of the development process, sensitometric measurement was performed using a PDA-65 type densitometer (manufactured by Konica Corporation).

Sensitivity was defined based on the reciprocal of the exposure dose giving a density of 0.75, and sample N processed 10 minutes after exposure.
o. The sensitivity of 1 was set as 100 and expressed as a relative value. The contribution ratio of sulfur sensitization was the same as that of the sample using the silver halide emulsion subjected only to the sulfur sensitization, the same sulfur sensitizer was used, and the halogen sensitized by the chemical sensitization by using the gold sensitizer together. It was determined based on the sensitivity obtained by processing the sample using the silver halide emulsion and 10 minutes after the exposure. The contribution of sulfur sensitization of the silver halide emulsion subjected only to sulfur sensitization was set to 100%.

The leg gradation is indicated by the slope of a straight line connecting the points of density 0.3 and 0.8 of the sensitometry curve. The results are shown in Table 1 below. The processing steps are shown below.

Processing step Temperature Time Color development 35.0 ± 0.3 ° C. 45 seconds Bleach fixing 35.0 ± 0.5 ° C. 45 seconds Stabilization 30-34 ° C. 90 seconds Dry 60-80 ° C. 60 seconds Development The composition of the treatment liquid is shown below.

[Color developer] Pure water 800 ml Triethanolamine 10 g N, N-diethylhydroxylamine 5 g Potassium bromide 0.02 g Potassium chloride 2 g Potassium sulfite 0.3 g 1-Hydroxyethylidene-1,1-diphosphonic acid 1 0.0 g Ethylenediaminetetraacetic acid 1.0 g Catechol-3,5-disulfonic acid disodium salt 1.0 g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 4.5 g Fluorescence enhancement Whitening agent (4,4'-diaminostilbene sulfonic acid derivative) 1.0 g Potassium carbonate 27 g Water is added to bring the total volume to 1 liter, and the pH is adjusted to 10.10.

[Bleaching Stabilizer] Ethylenediaminetetraacetic acid ammonium ferric dihydrate 60 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml Ammonium sulfite (40% aqueous solution) 27.5 millitorr Liter, pH = 5 with potassium carbonate or glacial acetic acid. Adjust to 7.

[Stabilizing Liquid] 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g ethylene glycol 1.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 g ethylenediaminetetraacetic acid 1. 0 g Ammonium hydroxide (20% aqueous solution) 3.0 g Optical brightener (4,4'-diaminostilbene sulfonic acid derivative) 1.5 g Water was added to make the total volume 1 liter, and pH = 7 with sulfuric acid or potassium hydroxide. Adjust to 0.

[0127]

[Table 1]

In Table 1, Comparative Sample No. 3 and comparative sample No. 1 and No. Comparing No. 2, compared with the sample using the emulsion only subjected to sulfur sensitization, the leg gradation of the sample using the emulsion combined with gold sensitization is higher and the sensitivity is higher, but It can be seen that there is a defect that the gradation of the legs changes due to the time change until development. Furthermore, sulfur sensitization was performed by triethylthiourea, 1,3, -diphenylthiourea,
Change to sulfur alone, change the amount of gold sensitizer and the time of addition,
It is understood that the effect of the present invention is preferably obtained when the contribution ratio of sulfur sensitization is within the range of the present invention.

Example 2 A paper support was prepared by laminating high-density polyethylene on both sides of paper pulp having a basis weight of 180 g / m ² . However, on the side on which the emulsion layer was coated, a molten polyethylene containing 15% by weight of surface-treated anatase type titanium oxide dispersed therein was laminated to prepare a reflective support. Each layer having the constitution shown below was coated on this reflective support to prepare a multilayer silver halide photographic light-sensitive material, Sample 101. The coating liquid was prepared as follows.

26.7 g of a yellow coupler (Y-1),
Dye image stabilizer (ST-1) 10.0 g, dye image stabilizer (ST-2) 6.67 g, additive (HQ-1)
0.67 g and high boiling organic solvent (DNP) 6.67 g
To the solution, add 60 ml of ethyl acetate and dissolve.
1 containing 9.5 ml of surfactant (SU-1)
220 ml of a 0% gelatin aqueous solution was emulsified and dispersed using an ultrasonic homogenizer to prepare a yellow coupler dispersion.

This dispersion was mixed with the blue-sensitive silver halide emulsion (containing 8.68 g of silver) Em-B ₁ prepared in Example 1, and 6% of a 5% aqueous solution of the anti-irradiation dye AI-3 was added. 0.7 ml was added to prepare a coating solution for the first layer. The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. Further, as a hardener, (H-1) was added to the second and fourth layers, and (H-2) was added to the seventh layer. Surfactants (SU-2) and (SU-3) were added as coating aids to adjust the surface tension. The layer structure is as follows.

Seventh layer (protective layer) Gelatin 1.00 g / m ² Antifungal agent (F-1) 0.002 g / m ²

Sixth layer (UV absorber layer) Gelatin 0.40 g / m ² UV absorber (UV-1) 0.10 g / m ² UV absorber (UV-2) 0.04 g / m ² UV absorber (UV-3) 0.16 g / m ² anti-stain (HQ-1) 0.01 g / m ² DNP 0.20 g / m ² PVP 0.03 g / m ² anti-irradiation dye (AI-1) 0. 02 g / m ²

Fifth layer (red-sensitive layer) Gelatin 1.30 g / m ² Red-sensitive silver chlorobromide emulsion (Em-R ₁ ) 0.21 g / m ² Cyan coupler (C-1) 0.42 g / m ² Dye image stabilizer (ST-1) 0.20 g / m ² stain inhibitor (HQ-1) 0.01 g / m ² HBS-1 0.20 g / m ² DOP 0.20 g / m ²

[0135] The fourth layer (ultraviolet absorber layer) Gelatin 0.94 g / m ² UV absorbent (UV-1) 0.28g / m 2 UV absorbent (UV-2) 0.09g / m 2 UV absorber (UV-3) 0.38 g / m ² stain inhibitor (HQ-1) 0.03 g / m ² DNP 0.40 g / m ² anti-irradiation dye (AI-2) 0.01 g / m ²

Third Layer (Green Sensitive Layer) Gelatin 1.40 g / m ² Green-sensitive silver chlorobromide emulsion (Em-G ₁ ) 0.17 g / m ² Magenta coupler (M-1) 0.35 g / m ² Dye image stabilizer (ST-3) 0.15 g / m ² Dye image stabilizer (ST-4) 0.15 g / m ² Dye image stabilizer (ST-5) 0.15 g / m ² DNP 0.20 g / m ²

[0137] The second layer (intermediate layer) Gelatin 1.20 g / m ² Stain preventing agent ^{(HQ-2) 0.12g / m} 2 DIDP 0.15g / m 2 fungicide (F-1) 0.002 g / m ² Irradiation prevention dye (AI-3) 0.01 g / m ²

First layer (blue photosensitive layer) Gelatin 1.20 g / m ² Blue-sensitive silver chlorobromide emulsion (Em-B ₁ ) 0.26 g / m ² Yellow coupler (Y-1) 0.80 g / m ² Dye image stabilizer (ST-1) 0.30 g / m ² Dye image stabilizer (ST-2) 0.20 g / m ² Stain inhibitor (HQ-1) 0.02 g / m ² DNP 0.20 g / m ² Support Polyethylene laminated paper The addition amount of silver halide emulsion is shown in terms of silver.

[0139]

[Chemical 4]

[0140]

[Chemical 5]

[0141]

[Chemical 6]

[0142]

[Chemical 7]

[0143]

[Chemical 8]

[0144]

[Chemical 9]

(Preparation Method of Blue-Sensitive Silver Halide Emulsion) The same emulsion as the emulsion (Em-B ₁ ) described in Example 1 was used.

(Preparation Method of Green-Sensitive Silver Halide Emulsion)
(A solution) and (B solution) addition time and (C solution) and (D solution)
In the same manner as EMP-1 except that the addition time of
Average particle size 0.43 μm, coefficient of variation (S / R) = 0.0
8. Monodisperse cubic emulsion E having a silver chloride content of 99.5 mol%
MP-2 was obtained. EMP-2 was chemically ripened at a temperature of 55 ° C. for 120 minutes using the following compound in accordance with the formulation 1 described in Example 1 to obtain a green-sensitive silver halide emulsion (Em-G ₁ ).
Got Sodium thiosulfate 1.5 mg / mol AgX Chloroauric acid 1.0 mg / mol AgX Stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX Sensitizing dye GS-1 4 × 10 ⁻⁴ mol / mol AgX

(Method for preparing red-sensitive silver halide emulsion)
(A solution) and (B solution) addition time and (C solution) and (D solution)
In the same manner as EMP-1 except that the addition time of
Average particle size 0.50 μm, coefficient of variation (S / R) = 0.0
8. Monodisperse cubic emulsion E having a silver chloride content of 99.5 mol%
MP-2 was obtained. EMP-3 was chemically ripened for 90 minutes at 60 ° C. according to the formulation 1 described in Example 1 using the following compound to obtain a red-sensitive silver halide emulsion (Em-R ₁ ). Sodium thiosulfate 1.8 mg / mol AgX Chloroauric acid 2.0 mg / mol AgX Stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX Sensitizing dye RS-1 1 × 10 ⁻⁴ mol / mol AgX

Next, in the preparation of the emulsion (EMP-2), an emulsion (EMP-4) was prepared in the same manner except that the exemplified compound (5) of the heavy metal compound was added to the solution C, and the heavy metal compound was prepared from the solution C. An emulsion (EMP-5) was prepared in the same manner except that the exemplified compound (6) was removed. Exemplified compound (5)
Was added so as to be 10 ⁻⁶ mol per mol of the final silver halide. Using these two emulsions, a green-sensitive emulsion (Em-G ₁ ) having the same formulation as the green-sensitive emulsion (Em-G ₁ ) was prepared.
G ₂ ) and (Em-G ₃ ) were prepared.

Next, in the preparation of a green-sensitive emulsion, as a sulfur sensitizer, triethylthiourea (1.80 × 10 ^-6 mol / mol AgX), 1, was used instead of sodium thiosulfate.
3-diphenylthiourea (1.80 × 10 ⁻⁶ mol / mol AgX) and simple substance of sulfur (0.3 mg / mol AgX) were chemically aged according to Formula 2 described in Example 1, From the emulsions (EMP-2), (EMP-4) and (EMP-5) described above to green-sensitive emulsions (Em-G ₄ ).
Was prepared - the (Em-G _12). The contents of the emulsion are shown in Table 2 below.
Shown in.

[0150]

[Table 2] Emulsion No. Sulfur sensitizer Heavy metal compound Em-G ₁ sodium thiosulfate Exemplified compound (6) Em-G ₂ sodium thiosulfate Exemplified compound (5) + (6) Em-G ₃ Sodium thiosulfate None Em-G ₄ triethylthiourea Exemplified compound (6) Em-G ₅ triethylthiourea exemplified compound (5) + (6) Em -G 6 triethylthiourea without Em-G ₇ Jifeniruchi urea exemplified compound (6) Em-G ₈ Jifeniruchi urea exemplified compound (5) + (6) Em-G ₉ Diphenylthiurea None Em-G ₁₀ Triethylthiourea Exemplified Compound (6) Em-G ₁₁ Triethylthiourea Exemplified Compound (5) + (6) Em-G ₁₂ Triethylthiourea None

Next, in the preparation of Sample 101, the green-sensitive emulsions (Em-G ₁ ) were sequentially prepared from (Em-G ₂ ) to (Em-G ₂ ).
Samples 102 to 112 were prepared in the same manner except that the method was changed to ₁₂ ). Using these samples, first, in the same manner as in Example 1, the influence of the time from exposure to development processing on sensitivity and gradation was examined. The results are shown in Table 3. The contribution ratio of sulfur sensitization shown in the table was determined according to the method described in Example 1.

[0152]

[Table 3]

As is clear from Table 3, Comparative Sample 10
In Nos. 1, 102, and 103, when a silver halide emulsion sensitized with a sulfur sensitizer and a gold sensitizer even when a heavy metal compound was contained was used, the sensitivity and gradation of the gradation were changed by changing the time from exposure to development. It can be seen that the fluctuation increases. Further, comparative samples 103 and 10 which do not contain the heavy metal compound.
It can be seen that in Nos. 6, 109 and 112, the sensitivity is low and the gradation becomes soft.

In contrast to these comparative samples, the sample using the silver halide emulsion of the present invention has high sensitivity and
It can be seen that variations in sensitivity and gradation are small. Next, the exposure time after exposure was adjusted to 10 minutes, and the exposure time was 0.01,
The change in sensitivity was evaluated by changing it for 0.5 and 10 seconds. The results are shown in Table 4. Here, the sensitivity was expressed as a relative value with 100 being the sensitivity at an exposure time of 0.5 seconds.

[0155]

[Table 4]

As is clear from Table 4, the exposure time is 0.5
Compared with the second sample, the sensitivity decreases remarkably as the exposure time becomes longer, but the sample containing the heavy metal compound in the silver halide emulsion of the present invention shows less decrease in sensitivity than the comparative sample containing no heavy metal compound. . On the other hand, in the case of short-time exposure, although the fluctuation range is small, the sensitivity tends to be high, but it can be seen that the sensitivity fluctuation is reduced by using the silver halide emulsion containing the heavy metal compound according to the present invention.

It is understood that the above effects are further enhanced when the chemical sensitization method according to the present invention is used. As described above, the technique of using a heavy metal compound, which is effective for improving the sensitivity variation caused by the change of the exposure time, also shows the sensitivity and gradation of the latent image variation from the exposure to the development in a relatively short time. Although it has a drawback of being changed, it is understood that this is improved by the present invention, and further, the sensitivity is improved and the sensitivity fluctuation due to the change of the exposure time is also improved.

[0158]

The present invention has a gold sensitization contribution rate of 20% to 80%.
The silver halide photographic light-sensitive material obtained by using a silver halide emulsion containing a heavy metal, which is chemically sensitized to have a high sensitivity, has high sensitivity and is excellent in sensitivity variation and gradation variation after exposure. Things are obtained. Therefore, by using the silver halide photographic light-sensitive material of the present invention, a high quality and stable image can be obtained by short-time processing.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Go Ikeda No. 1 Sakura-cho, Hino City, Tokyo Konica Stock Company

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material having on a support at least one silver halide emulsion layer containing photosensitive silver halide grains chemically sensitized by a sulfur sensitizer and a gold sensitizer. In, the contribution of the sensitization by the sulfur sensitizer to the sensitivity of the silver halide emulsion layer does not eliminate the gold sensitizing effect when the sensitivity of the silver halide emulsion layer eliminates the effect of gold sensitization. 20% to 8% of the sensitivity in the state
The photosensitive silver halide grains are chemically sensitized so that the content of the photosensitive silver halide grains becomes 0%.
It contains at least mol% of silver chloride, and is contained in the photosensitive silver halide grains inside and / or on the surface of the periodic table.
A silver halide photographic light-sensitive material, which is a photosensitive silver halide grain containing at least one of a Group III metal, a Group II transition metal of the periodic table, lead, rhenium, molybdenum, tungsten, and chromium.