JP2578206B2 - Silver halide photographic material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material, and more particularly, to a silver halide photographic material which is reduced and sensitized during grain formation and has a specified amount of silver iodide on its surface. The present invention relates to a silver halide photographic material having high sensitivity and low fog, particularly having high sensitivity in a color sensitization region, containing photosensitive silver halide grains.

(Prior Art) The basic performance required of a silver halide emulsion for photography is high sensitivity, low fog and fine grain.

In order to enhance the sensitivity of the emulsion, (1) increasing the number of photons absorbed by one grain, (2) increasing the efficiency of converting photoelectrons generated by light absorption into silver clusters (latent images), And (3) it is necessary to increase the developing activity in order to effectively use the latent image formed. Increasing the size increases the number of absorbed photons per particle, but reduces the image quality. Increasing the development activity is also an effective means for increasing the sensitivity. However, in the case of parallel type development such as color development, graininess generally deteriorates. In order to increase the sensitivity without causing deterioration in graininess, it is most preferable to increase the efficiency of converting photoelectrons into a latent image, that is, to increase the quantum sensitivity. In order to increase the quantum sensitivity, it is necessary to remove inefficient processes such as recombination and latent image dispersion as much as possible. It is known that a reduction sensitization method in which small silver nuclei having no development activity are formed inside or on the surface of silver halide is effective for preventing recombination.

Also, James et al. Conducted a kind of reduction sensitization in which a coating film of an emulsion sensitized with gold and sulfur was subjected to vacuum degassing and then heat-treated in an atmosphere of hydrogen gas. It has been found that the sensitivity can be increased at a lower fog level as compared with the above. This sensitization method is well known as hydrogen sensitization and is effective as a sensitization means on a laboratory scale.
Furthermore, hydrogen sensitization is actually used in the field of astrophotography.

Attempts at reduction sensitization have long been considered. Carroll
(Carroll) in U.S. Pat. No. 2,487,850 for tin compounds, Lowe et al. For polyamine compounds in U.S. Pat. No. 2,512,925, and Fallens (Farence) for U.S. Pat. No. 789,823 for thiourea dioxide compounds. It is disclosed that it is useful as a reduction sensitizer. Further Co
llier is Photographic Science and Engine
ering 23: 113 (1979) compares the properties of silver nuclei produced by various reduction sensitization methods. She is dimethylamine borane, stannous chloride, hydrazine, high
A method of pH aging and low pAg aging was adopted. The method of reduction sensitization is further disclosed in U.S. Pat. Nos. 2,518,698, 3,201,254, 3,411,917, 3,779,777, and 3,930,867. Regarding the method of using the reducing agent as well as the selection of the reduction sensitizer, JP-B-57-33572 and JP-B-58-1410
And JP-A-57-179835. Further, techniques for improving the preservability of the emulsion sensitized by reduction are disclosed in JP-A-57-82831 and JP-A-60-178445.
Although much research has been conducted in this way, the sensitivity increase width was insufficient compared with the hydrogen sensitization in which the photosensitive material was treated with hydrogen gas under vacuum. This is the Journal of
Moisar in Imaging Science Vol. 29, p. 233 (1985)
(Moiser) et al.

Further, in the above-mentioned literature, conventionally known reduction sensitizers are listed, and ascorbic acid is described therein. However, compounds such as thiourea dioxide are preferred, and the examples also show thiourea dioxide, silver ripened, and hydrozine. Therefore, favorable properties of the ascorbic acid compound as a reduction sensitizer have not been found. For further contrivance, see JP-A-57-179835.
Issue.

However, in order to put reduction sensitization into practical use, it is necessary to overcome the problem of the storage stability of the photosensitive material. A technique for improving the storage stability of the reduction-sensitized emulsion is also disclosed in JP-A-57-82831.
No. 60-178445, but the level of improvement is not yet sufficient. At the same time, improvements in the storability of light-sensitive materials containing reduction-sensitized emulsions have been desired.

[Problems to be solved by the invention]

The prior art of reduction sensitization is insufficient for recent demands for high-sensitivity and high-quality photographic materials. The means of hydrogen sensitization also has a disadvantage that the sensitizing effect is lost if the photosensitive material is left in the air after the hydrogen sensitization. Therefore, it is difficult to use this sensitization method in the case of a photographic material in which a special device cannot be used.

Further, when color sensitization is performed, there is a problem that the increase in sensitivity due to reduction sensitization is reduced.

(Object of the Invention) An object of the present invention is to provide a silver halide photographic light-sensitive material having high sensitivity, low fog, and particularly high sensitivity in the color sensitization region. It is a second object of the present invention to provide a color photographic light-sensitive material which is less sensitive to natural radiation, has high sensitivity and has little fog.

[Means for solving the problem]

The object of the present invention has been achieved by the following silver halide photographic materials described in (1) to (6).

(1) Reduction sensitization during grain growth and at least one of gold sensitization, sulfur sensitization or noble metal sensitization in an optional step
A silver halide photographic light-sensitive material having on a support at least one silver halide emulsion layer containing silver halide grains having a silver iodide content of 5 mol% or more.

(2) The silver halide photographic material according to the above (1), which has been reduction-sensitized in the presence of at least one compound represented by the formula [I], [II] or [III].

[I] R-SO ₂ S-M [II] R-SO ₂ S-R ¹ [III] RSO ₂ S-Lm-SSO ₂ -R ^{2 In the} formula, R, R ¹ and R ² may be the same or different. Represents an aliphatic group, an aromatic group, or a heterocyclic group, and M represents a cation. L represents a divalent linking group, and m is 0 or 1.

The compounds of the general formulas [I] to [III] may be polymers containing a divalent group derived from the structure represented by any one of [I] to [III] as a repeating unit. When possible, R, R ¹ , R ² , and L may combine with each other to form a ring.

(3) The silver halide photographic material as described in the above item (1), which contains silver halide grains sensitized by gold and sulfur after reduction sensitization.

(4) The silver halide photographic material as described in (1) above, which has been reduction-sensitized with at least one of ascorbic acid or a derivative thereof.

(5) 5 silver halide grains per mole of silver halide
The silver halide photographic light-sensitive material according to the above (4), which has been subjected to reduction sensitization with from × 10 ^-5 mol to 1 × 10 ^-1 mol of ascorbic acid or a derivative thereof.

(6) The silver halide photographic material as described in (4) above, which has been subjected to reduction sensitization in the presence of at least one compound represented by the general formula [I], [II] or [III].

 Hereinafter, the present invention will be described in detail.

In the production of silver halide grains which is a feature of the present invention, reduction sensitization is performed during growth of silver halide grains. Here, "growing" means that the silver halide grains are undergoing physical ripening, and a water-soluble silver salt and a water-soluble alkali halide are being added (precipitation, Pr
ecipitation) also means that they are contained during the further precipitation step after reduction sensitization with these additions temporarily stopped.

The reduction sensitization of the present invention includes a method of adding a reduction sensitizer to a silver halide emulsion, a method of growing or ripening in a low pAg atmosphere of pAg 1 to 7 called silver ripening, and a method of pH 8 to 11 called high pH ripening. Growth or ripening in a high pH atmosphere. Also, two or more methods can be used in combination.

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

Stannous salts, amines and polyamines, hydrazine derivatives, formamidine sulfinic acid as reduction sensitizers,
Silane compounds, borane compounds and the like are known. 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 as reduction sensitizer,
Dimethylamine borane is a preferred compound. Since the addition amount of these reduction sensitizers depends on the emulsion production conditions, it is necessary to select the addition amount, but 10 ^-7 per mol of silver halide.
A range of 1010 ^-3 mol is suitable.

These reduction sensitizers are 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. Further, a reduction sensitizer may be added in advance to an aqueous solution 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 particularly preferable that the reduction sensitization of the present invention is performed by ascorbic acid or one of its derivatives.

Specific examples of ascorbic acid and its derivatives (hereinafter, referred to as “ascorbic acid compound”) include the following.

(A-1) L-ascorbic acid (A-2) L-sodium ascorbate (A-3) potassium L-ascorbate (A-4) DL-ascorbic acid (A-5) D-sodium ascorbate (A -6) L-ascorbic acid-6-acetate (A-7) L-ascorbic acid-6-palmitate (A-8) L-ascorbic acid-6-benzoate (A-9) L-ascorbic acid-6-di Acetate (A-10) L-ascorbic acid-5,6-O-isopropylidene To add the above ascorbic acid compound in the production process of the silver halide emulsion of the present invention, disperse them directly in the emulsion. Alternatively, it may be dissolved in a single or mixed solvent of water, methanol, ethanol and the like and added during the production process.

It is desirable to use a large amount of the ascorbic acid compound used in the present invention as compared with the amount in which a reduction sensitizer is conventionally preferably used. For example, Japanese Patent Publication No. 57-33572 states that the amount of the reducing agent does not usually exceed 0.75 × 10 ^-2 molar equivalents (g × 10 ⁻⁴ mol / Ag × mol) per g of silver ion. Amount (as ascorbic acid, 10 ^-7 to 10
^(-5 mol / Ag x mol) is effective in many cases. (The converted value is based on the inventors). US-2,487,
No. 850 describes "1.times.10.sup.- ^{7 to} 44.times.10.sup.- ⁶ mol as an addition amount in which a tin compound can be used as a reduction sensitizer". JP-A-57-179835 states that it is appropriate to use about 0.01 mg to about 2 mg of thiourea dioxide per mole of silver halide and about 0.01 mg to about 3 mg of stannous chloride. doing. The preferred amount of the ascorbic acid compound used in the present invention depends on factors such as the grain size of the emulsion, the halogen composition, the temperature of the emulsification preparation, the pH and the pAg, but is preferably from 5 × 10 ^-5 mol per mol of silver halide. 1 × 10
It is desirable to select from the range of ^-1 mol. It is more preferable to select from the range of 5 × 10 ^-4 mol to 1 × 10 ^-2 mol. It is particularly preferable to select from the range of 1 × 10 ⁻³ mol to 1 × 10 ⁻² mol.

The ascorbic acid compound of the present invention may be added at any stage of the emulsion production process, but a particularly preferable method is to add during the grain growth. It may be added to the reaction vessel in advance, but it is more preferable to add it at an appropriate time during particle formation. Alternatively, a reduction sensitizer may be added to an aqueous solution of a water-soluble silver salt or a water-soluble alkali halide in advance, and particles may be formed using these aqueous solutions. It is also a preferred method to add the solution of the reduction sensitizer in several portions as the grains are formed, or to add the solution continuously for a long time.

The method of reduction sensitization using the ascorbic acid compound of the present invention is more sensitive than conventionally known reduction sensitization methods,
Although excellent in fog and stability over time, combination with other reduction sensitization methods is more preferable in some cases. As a method for combining silver halide emulsions, a known reducing agent is added to a silver halide emulsion, and a low pA of pAg1 to 7 called silver ripening is used.
Growth or ripening in g atmosphere, high pH
Either a method of growing in a high pH atmosphere of pH 8-11 called ripening or a method of ripening can be selected.
Among these, the method of adding a reduction sensitizer is a preferable method since the level of reduction sensitization can be finely adjusted.

Stannous salts, amines and polyamines, hydrazine derivatives, formamidine sulfinic acid as reduction sensitizers,
Although silane compounds and borane compounds are known, ascorbic acid compounds give better results than these known reduction sensitizers.

In addition to the reduction sensitization of the present invention, chemical sensitization includes sulfur sensitization, gold sensitization, and noble metals of Group VIII of the periodic table (eg, Pd, P
Sensitization by (t, Id) and a combination of these sensitizations can be employed. Among them, gold sensitization or sulfur sensitization is preferable, and gold plus sulfur sensitization (also referred to as “gold-sulfur sensitization”) is particularly preferable. After reduction sensitization of the present invention,
Preferably, sulfur sensitization is performed.

When the compounds of the general formulas (I), (II) and (III) are described in more detail, when R, R ¹ and R ² are an aliphatic group, they may be saturated or unsaturated, linear, branched or cyclic; It is an aliphatic hydrocarbon group, preferably an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, or an alkynyl group, which may have a substituent. Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, hexadecyl, octadecyl,
Examples include cyclohexyl, isopropyl, and t-butyl.

Examples of the alkenyl group include allyl and butenyl.

Examples of the alkynyl group include propargyl and butynyl.

The aromatic group represented by R, R ¹ and R ² includes a monocyclic or condensed ring aromatic group, preferably having 6 to 20 carbon atoms, such as phenyl and naphthyl. These may be substituted.

The heterocyclic group represented by R, R ¹ and R ² is a 3- to 15-membered ring having at least one element selected from nitrogen, oxygen, sulfur, selenium and tellurium and having at least one carbon atom. And preferably a 3- to 6-membered ring, for example, pyrrolidine, piperidine, pyridine, tetrahydrofuran, thiophene, oxazole, thiazole, imidazole, benzothiazole, benzoxazole, benzimidazole, selenazole, benzoselenazole, tellurazole, triazole, benzotriazole, Examples include tetrazole, oxadiazole, and thiadiazole rings.

Examples of the substituent for R, R ¹ and R ² include an alkyl group (eg, methyl, ethyl, hexyl), an alkoxy group (eg, methoxy, ethoxy, octyl), an aryl group (eg, phenyl, naphthyl, tolyl), Hydroxy group, halogen atom (fluorine, chlorine, bromine, iodine), aryloxy group (for example, phenoxy), alkylthio group (for example, methylthio, butylthio), arylthio group (for example, phenylthio), acyl group (for example, acetyl, propionyl, Butyryl, valeryl), sulfonyl group (eg, methylsulfonyl, phenylsulfonyl), acylamino group (eg, acetylamino, benzoylamino), sulfonylamino group (eg, methanesulfonylamino, benzenesulfonylamino), acyloxy group (eg, aceto Shi, benzoxy), a carboxyl group, a cyano group, a sulfo group, an amino group, -SO ₂ SM
And —SO ₂ R ¹ groups.

The divalent linking group represented by L is an atom or an atomic group containing at least one selected from C, N, S and O. Specifically, an alkylene group, an alkenylene group,
Alkynylene group, arylene group, -O-, -S-, -NH
-, - CO -, - SO 2 - is made of a single or combination of such.

L is preferably a divalent aliphatic group or a divalent aromatic group. The divalent aliphatic group of L for example _{CH 2 n (n = 1~12)} , -CH 2 -CH = CH-CH 2 -, -CH 2 C≡CCH 2 -, A xylylene group, and the like. Examples of the divalent aromatic group for L include a phenylene group and a naphthylene group.

These substituents may be further substituted with the substituents described above.

M is preferably a metal ion or an organic cation. Examples of the metal ion include a lithium ion, a sodium ion, and a potassium ion. As organic cations, ammonium ions (ammonium, tetramethylammonium, tetrabutylammonium, etc.),
Phosphonium ion (tetraphenylphosphonium),
And guanidyl groups.

When the general formulas (I) to (III) are polymers,
Examples of the repeating unit include the following.

These polymers may be homopolymers or copolymers with other copolymerized monomers.

Specific examples of the compound represented by the general formula [I], [II] or [III] are shown in Table A, but are not limited thereto.

The compound of the general formula (I) is disclosed in JP-A-54-1019;
72,211; Journal of Organic Chemistry
Of Organic Chemistry) 53, 396 pages (198
8) and Chemical Abstracts (Chemical Abstracts), vol. 59, 9776e.

The compound represented by the general formula [I], [II] or [III] is preferably added in an amount of 10 ^-7 to 10 ^-1 mol per mol of silver halide. From 10 ^-6 to 10 ^-2 , especially from 10 ^-5
The addition amount of 10 ^-3 mol / mol Ag is preferable.

In order to add the compounds represented by the general formulas [I] to [III] during the production process, a method usually used for adding an additive to a photographic emulsion can be applied. For example, a water-soluble compound is an aqueous solution having an appropriate concentration, and a compound that is insoluble or hardly soluble in water is a suitable organic solvent that is miscible with water, for example, alcohols, glycols, ketones, esters, amides and the like. Among them, it can be dissolved in a solvent that does not adversely affect the photographic properties and added as a solution.

The compound represented by the compound [I], [II] or [III] may be present at any stage of reduction sensitization during grain growth. Preferably, the compound is added before or during the reduction sensitization. It is particularly preferable to add so as to coexist with the reduction sensitizer.

The general formula of the compound most preferable for the present invention is a compound represented by the general formula [I].

It was completely unexpected that it was found that the effect of the reduction sensitization was remarkable when the surface of the silver halide grains of the present invention contained 5 mol% or more of silver iodide. Various methods conventionally known as a method for controlling the silver iodide content near the surface of the grains can be employed. A method of further adding an aqueous solution of a water-soluble silver salt and an aqueous solution of a halide containing a water-soluble iodide to silver halide grains grown in the presence of a protective colloid; The addition method can be selected from a method in which a poorly soluble iodide such as silver iodide or silver iodobromide is added and ripened. Alternatively,
A method in which iodide is distributed near the surface by physically ripening silver halide grains containing iodide can also be used.

5 to 30 contained in the surface of the silver halide grains of the present invention.
In the case of cubic and octahedral crystals, it is preferable that the mol% of silver iodide be as uniform as possible on the surface. It is preferred that the grains have a layered structure in which the entire surface is covered by a layer containing silver iodide. However, (111) and (100) planes coexist14
In a grain such as a facet or a grain having a principal plane and a side face coexisting like a tabular grain, a case where only a specific face is mainly covered with a layer containing silver iodide is also a preferred embodiment of the present invention. In other words, the case where the surface of the grain is partially but not entirely covered with the layer containing silver iodide also belongs to the present invention.

When the surface of the present invention forms a layer containing 5 mol% or more of silver iodide, a spectral sensitizing dye such as cyanine or merocyanine or an antifoggant or stabilizer such as a mercapto compound, an azole compound or an azaindene compound is present. This is the preferred method. Similarly, it may be preferable to use a silver halide solvent such as thiocyanic acid / thioether / ammonia.

The silver iodide content on the surface of the silver halide grains of the present invention can be detected by various surface elemental analysis means. It is useful to use methods such as XPS, Auger electron spectroscopy, and ISS. The simplest and most accurate means is XPS (X-ray
Photoelectron spectroscopy), and the surface silver iodide content of the present invention is defined by the value measured by this method.

It is said that the depth analyzed by XPS (X-ray Photoelectron Spectroscopy) surface analysis is about 10 °.

Regarding the principle of the XPS method used for analyzing the iodine content near the surface of silver halide grains, Junichi Aihara et al., “Electron spectroscopy” (Kyoritsu Library 16, published by Kyoritsu Shuppan, Showa 53)
Year) can be referred to.

The standard method for measuring XPS is to use Mg-Kα as excited X-rays, and to use iodine (I) and silver (Ag) photoelectrons (usually I-
3d _5/2 , Ag-3d _5/2 ).

To determine the iodine content, a calibration curve of the intensity ratio of the photoelectrons of iodine (I) and silver (Ag) (intensity (I) / intensity (Ag)) using several types of standard samples with known iodine contents. And can be determined from this calibration curve. In the silver halide emulsion, XPS must be measured after the gelatin adsorbed on the surface of the silver halide grains is decomposed and removed by a protease or the like, and then the XPS measurement must be performed. Silver iodide refers to a silver iodide having a silver iodide content of 5 mol% or more when the emulsion grains contained in one emulsion are analyzed by means of elemental analysis of the surface. In this case, when two or more types of emulsions are clearly mixed, it is necessary to perform an appropriate pretreatment such as a centrifugal separation method or another method and then analyze the same type of emulsion. More preferably, it refers to an emulsion having a silver iodide content of 5 to 30 mol% when standard XPS measurement is performed.

The effect of the present invention is remarkable when the surface of the grains contains 5 mol% or more of silver iodide.
More preferred are grains whose surface contains 10 to 15 mol% of silver iodide.

The surface halogen composition other than silver iodide is preferably silver bromide, but may contain 10 mol% or less of silver chloride.

The average silver halide composition of the whole reduction sensitized silver halide grains of the present invention is silver iodobromide or silver iodochlorobromide containing 1 to 30 mol% of silver iodide. Preferably 7 to
It contains 20 mol% of silver iodide and may contain 10 mol% or less of silver chloride.

In the emulsion layer of the photographic light-sensitive material of the present invention, silver iodobromide and silver iodide-collected silver which have not been subjected to reduction sensitization can be used alone or in combination with the silver halide grains of the present invention. Preferred silver halides are silver iodobromide or silver iodochlorobromide containing up to 30 mol% of silver iodide.

The silver halide grains used in the present invention may be normal crystals that do not contain twin planes, but may be prepared as described in the Photographic Society of Japan, Basic Silver Salt Photography of the Photographic Industry (Corona Co., p. Single twins containing one crystal plane, parallel multiple twins containing two or more parallel twin planes, non-parallel multiple twins containing two or more non-parallel twin planes, etc. In the case of a normal crystal, a cube consisting of (100) planes,
Octahedron consisting of (111) faces, Japanese Patent Publication No. 55-42737,
-222842. Dodecahedral particles having a (110) plane can be used. Furthermore, Journal of Imaging
(H11) plane particle represented by (211), (hh1) plane particle represented by (331), (hk0) plane represented by (210) plane, as reported in Science Vol. 30, p. 247, 1986 The particles and the (hk1) plane particles represented by the (321) plane also need to be devised in the preparation method, but can be selected and used according to the purpose.
A tetrahedral particle in which (100) and (111) planes coexist in one particle, a particle in which (100) and (110) planes coexist, or (11
Particles in which two surfaces or many surfaces coexist, such as particles in which 1) and (110) surfaces coexist, can be selected and used according to the purpose.

The particle size of the silver halide grains of the present invention to be reduction-sensitized or used in combination may be fine grains of 0.1 μm or less or large grains having a projected area diameter of up to 10 μm, and have a narrow distribution. A monodisperse emulsion or a polydisperse emulsion having a wide distribution may be used.

Narrow particle size distribution such that 80% or more of all particles fall within ± 30% of average particle size by number or weight of particles.
So-called monodisperse silver halide emulsions can be used in the present invention. In order to satisfy the target gradation of the light-sensitive material, two or more monodispersed silver halide emulsions having different grain sizes are mixed in the same layer or different layers in an emulsion layer having substantially the same color sensitivity. Can be applied in layers. Further, two or more kinds of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion can be used as a mixture or as a mixture.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Grafkid, published by Paul Montell (P. Glafkides, Ch.
imie et Physique Photographique Paul Montel, 196
7), “Digital Photographic Emulsion Chemistry”, published by Focal Press (GFDuffin, Photographic Emulsion Chemistry)
(Focal Press, 1966), "Production and Coating of Photographic Emulsion", by Zerikman et al., Published by Focal Press (VLZelikman et.
al, Making and Coating Photographic Emulsion, Focal
Press, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method of reacting a soluble silver salt and a soluble halide is a one-side mixing method, a simultaneous mixing method,
Any of these combinations and the like may be used. A method of forming grains in the presence of excess silver ions (a so-called reverse mixing method) can also be used. As one type of the double jet method, a method in which pAg in a liquid phase in which silver halide is formed is kept constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained.

The silver halide emulsion comprising the regular grains,
It is obtained by controlling pAg and pH during particle formation.
See, for example, Photographic Science and Engineering
Engineering, Vol. 6, pp. 159-165 (1962); Journal of Photography Science (Journal o)
f Photographic Science), 12, 242-251 (196
4), U.S. Patent No. 3,655,394 and UK Patent No. 1,413,74
It is described in No. 8.

Tabular grains having an aspect ratio of 3 or more can also be used in the present invention. Tabular grains are described in Cleve, Photography Theory and Pra
ctice (1930), p. 131; Gatov, Photographic Science and Engineering (Gutoff, Pho
tographic Science and Engineering), Vol. 14, 248-2
57 pages (1970); U.S. Patent Nos. 4,434,226 and 4,414,310
No. 4,433,048, No. 4,439,520 and British Patent No. 2,
It can be easily prepared by the method described in JP-A No. 112,127 or the like. When tabular grains are used, there are advantages such as an increase in covering power and an increase in color sensitization efficiency by a sensitizing dye, and are described in detail in U.S. Pat. No. 4,434,226 cited above.

As the emulsion of the present invention, tabular grains are preferred. Particularly, tabular grains in which grains having an aspect ratio of 3 to 8 account for 50% or more of the total projected area are preferred.

The crystal structure may be uniform, the inside and the outside may be composed of different halogen compositions, or may have a layered structure. These emulsion grains are described in GB 1,027,146.
And U.S. Pat. Nos. 3,505,068 and 4,444,877 and Japanese Patent Application No. 58-248469. Further, silver halides having different compositions may be bonded by epitaxial bonding, or may be bonded to a compound other than silver halide such as, for example, silver rhodanate or lead oxide.

The silver halide emulsion of the present invention preferably has a distribution or a structure with respect to the halogen composition in the grains. Typical examples are JP-B-43-13162 and JP-A-61-2.
These are core-shell type or double structure type particles having a halogen composition in which the inside and the surface of the grains have different halogen compositions, as disclosed in JP-A No. 15540, JP-A-60-222845 and JP-A-61-75337. In such particles, the shape of the core portion and the entire shape with the shell may be the same or different. Specifically, the core portion has a cubic shape, and the shape of the shell-containing particles may be cubic or octahedral. Conversely, the core may be octahedral, and the particles with shells may have a cubic or octahedral shape. In addition, although the core portion is a clear regular particle, the shape of the particle with a shell may be slightly distorted or irregular. Further, instead of a mere double structure, a triple structure as disclosed in JP-A-60-222844 or a multilayer structure more than that, or a different composition on the surface of a core-shell double structure particle may be used. Silver halide.

In order to give a structure inside the particle, not only the above-described wrapping structure but also a particle having a so-called bonding structure can be produced. These examples are described in JP-A-59-133540, JP-A-58-108526, EP199290A2, JP-B-58-24772,
59-16254. The crystal to be bonded can be formed by bonding to the edge, corner, or face of the host crystal with a composition different from that of the host crystal. Such a junction crystal can be formed even if the host crystal is uniform in the halogen composition or has a core-shell structure.

In the case of a bonding structure, a combination of silver halides is naturally possible, but a silver salt compound having no rock salt structure such as silver rhodanate or silver carbonate can be combined with silver halide to form a bonding structure. A non-silver salt compound such as PbO may be used as long as it can form a junction structure.

In the case of grains such as silver iodobromide having these structures, for example, in core-shell type grains, the core portion preferably has a higher silver iodide content than the shell portion. Conversely, grains having a low silver iodide content in the core portion and a high shell portion may be used. Similarly, grains having a junction structure may be grains having a high silver iodide content in the host crystal and relatively low silver iodide content in the junction crystal, or vice versa.

In addition, the boundary portion having a different halogen composition of the grains having these structures may be a clear boundary, or may be an unclear boundary formed by a mixed crystal due to a composition difference. It may have a structural change.

The silver halide emulsion used in the present invention is EP-0096727B1, E
P-0064412B1 and other treatments for imparting roundness to particles, or DE-2306447C2, JP-A-60-221
Modification of the surface as disclosed in 320 may be performed.

The silver halide emulsion used in the present invention is preferably a surface latent image type, but an internal latent image type emulsion may be used by selecting a developing solution or development conditions as disclosed in JP-A-59-133542. it can. A shallow internal latent image type emulsion covered with a thin shell can also be used depending on the purpose.

Silver halide solvents are useful to promote ripening.
For example, it is known to have an excess of halogen ions in the reactor to promote ripening. It is therefore clear that ripening can be promoted simply by introducing a halide salt solution into the reactor. Other ripening examples may be used, these ripening agents may be incorporated in their entirety in the dispersion medium in the reactor before adding the silver and halide salts, and one or more ripening agents may be used. And a peptizer may be added and introduced into the reactor. As another variant, the ripening agent can be introduced independently during the halide salt and silver salt addition steps.

As the ripening agent other than the halogen ion, ammonia or an amine compound, a thiocyanate salt, for example, an alkali metal thiocyanate salt, particularly a sodium and potassium thiocyanate salt, and an ammonium thiocyanate salt can be used.

The silver halide grains of the present invention may be subjected to at least one of sulfur sensitization, gold sensitization, or noble metal sensitization in addition to reduction sensitization, at any step of the step of producing a silver halide emulsion, typically the step of grain formation. I will give it. These chemical sensitizations depend on the composition of the emulsion grains.
Depending on the structure / shape and the intended use in which the emulsion is used, it is typically carried out in a grain growth stage after the reduction sensitization of the present invention. There is a case where a chemical sensitizing nucleus is embedded in the inside of a grain, a case where the chemical sensitizing nucleus is embedded in a position shallow from the grain surface, or a case where a chemical sensitizing nucleus is formed on the surface. The effect of the present invention is effective in any case, but particularly preferable is a case where a chemical sensitizing nucleus is formed near the surface.
That is, the surface latent image type emulsion is more effective than the internal latent image type emulsion.

Chemical sensitization which can be preferably carried out in the present invention other than reduction sensitization (hereinafter, also simply referred to as chemical sensitization) is gold sensitization, sulfur sensitization or noble metal sensitization alone or in combination. Author, The Photographic Process, 4th Edition, Macmillan, 1977, (THJames, Th
e Theory of the Photographic Process, 4th ed, Ma
cmillan, 1977), using active gelatin as described on pages 67-76, and in Research Disclosure 120, April 1974, 12008; Research Disclosure, 34, June 1975. , 13452, U.S. Pat.Nos. 2,642,361, 3,297,446, 3,772,031,
Nos. 3,857,711, 3,901,714, 4,266,018, and 3,904,415, as well as British Patent No. It can be platinum, palladium, iridium or a combination of several of these sensitizers. These chemical sensitizations are most preferably in the presence of a gold compound and a thiocyanate compound, and also in US Pat.
The reaction is carried out in the presence of a sulfur-containing compound described in 3,857,711, 4,266,018 and 4,054,457 or a sulfur-containing compound such as hypo, thiourea-based compound and rhodanine-based compound. 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. 2,131,038, 3,411,914, 3,55
No. 4,757, JP-A-58-126526, and the aforementioned "Photographic Emulsion Chemistry" by Duffin, pp. 138-143.

In the emulsion of the present invention, no defect occurs even when another chemical sensitization is used in combination with the reduction sensitization. In particular, it has been difficult in the past to use gold sensitization and reduction sensitization together because of an increase in fog. However, the emulsion of the present invention exhibits a preferable effect even when gold sensitization is used in combination. A preferred amount of the gold sensitizer is 1 × 10 ^-4 to 1 mol / mol of silver halide.
1 × 10 ⁻⁷ mol, more preferably 1 × 10 ^{−5 to} 5
× 10 ^-7 mol.

The preferred amount of sulfur sensitizer used for the silver halide grains of the present invention is 1 × 10 ^-4 to 10 ^-7 per mol of silver halide.
Mole, more preferably 1 × 10 ^{-5 to} 5 × 10 ^-7 mole.

In gold / sulfur sensitization, the above conditions are preferably used in combination.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles,
Mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (especially 1-phenyl-5-mercaptotetrazole), etc .; mercaptopyrimidines; mercaptotriazines Thioketo compounds such as oxadolinthione; azaindenes such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetraazaindenes), pentaazaindenes and the like; Many compounds known as antifoggants or stabilizers can be added. For example, U.S. Pat.
Nos. 3,982,947 and JP-B-52-28,660 can be used.

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. The dyes used include cyanine dyes, merocyanine dyes, composite cyanine dyes, composite merocyanine dyes, holopolar cyanine dyes, hexyanine dyes,
Styryl dyes and hemioxonol dyes are included. 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; The nucleus of the aromatic hydrocarbon ring fused to the nucleus, namely, indolenine nucleus, benzindolenin nucleus, indole nucleus
A benzoxadol nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus and the like can be applied. These nuclei may be substituted on carbon atoms.

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

These sensitizing dyes may be used alone or in combination, and a combination of sensitizing dyes is often used particularly for supersensitization. Representative examples are U.S. Pat.Nos. 2,688,545, 2,977,229, 3,397,060 and 3,5
22,052, 3,527,641, 3,617,293, 3,628,96
No. 4, 3,666,480, 3,672,898, 3,679,428,
3,703,377, 3,769,301, 3,814,609, 3,8
37,862, 4,026,707, British Patent 1,344,281, 1,
507,803, JP-B-43-4936 and JP-B-53-12,375, and JP-A-52-110,618 and JP-A-52-109,925.

Along with 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 been known to be useful. Most commonly, it is performed after completion of chemical sensitization but before coating, but as described in U.S. Pat.Nos. 3,628,969 and 4,225,666, it is added at the same time as a chemical sensitizer and spectrally sensitized. Sensitization can be carried out simultaneously with chemical sensitization or prior to chemical sensitization as described in JP-A-58-113,928. Sensitization can also be started. Furthermore, separately adding these compounds as taught in U.S. Pat.No.4,225,666,
That is, it is also possible to add a part of these compounds prior to chemical sensitization and add the remainder after chemical sensitization,
At any time during silver halide grain formation, including the method taught in U.S. Pat. No. 4,183,756.

The addition amount is 4 × 10 ^-6 to 8 × per mol of silver halide.
Although it can be used in an amount of 10 ^-3 mol, a silver halide grain size of about 5 × 10 ^-5 to 2
× 10 ^-3 mol is more effective.

The above-mentioned various additives are used in the photosensitive material according to the present technology, but other 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.
(1976, November), and the relevant locations are summarized in the table below.

Various color couplers can be used in the present invention, and specific examples thereof are described in the patents described in the aforementioned Research Disclosure (RD) No. 17643, VII-CG.

As a yellow coupler, for example, U.S. Pat.
No. 501, No. 4,022,620, No. 4,326,024, No. 4,40
No. 1,752, JP-B-58-10739, UK Patent No. 1,425,020
And No. 1,476,760 are preferred.

As the magenta coupler, 5-pyrazolone and pyrazoloazole compounds are preferable.
4,310,619, 4,351,897, EP 73,636,
U.S. Patent Nos. 3,061,432 and 3,725,067, Research
Disclosure No. 24220 (June 1984)
-33552, Research Disclosure No.24230 (1
Jun. 984), JP-A-60-43659, U.S. Pat.
Nos. 0 and 4,540,654 are particularly preferred.

Cyan couplers include phenolic and naphthol couplers, for example, U.S. Pat.
No. 4,146,396, No. 4,228,233, No. 4,296,20
No. 0, 2,369,929, 2,801,171, 2,772,1
No. 62, No. 2,895,826, No. 3,772,002, No. 3,758,
No. 308, No. 4,334,011, No. 4,327,173, West German Patent Publication No. 3,329,729, European Patent No. 121,365A, U.S. Patent No. 3,446,622, No. 4,333,999, No. 4,451,559,
Preferred are those described in US Pat. No. 4,427,797 and European Patent No. 161,626A.

A colored coupler for correcting unnecessary absorption of a coloring dye is described in, for example, Research Disclosure No. 17643.
VII-G, U.S. Pat.No. 4,163,670, JP-B-57-3941
3, U.S. Pat. Nos. 4,004,929 and 4,138,258, and British Patent 1,146,368 are preferred.

As a coupler in which the coloring dye has an appropriate diffusivity,
For example, U.S. Patent No. 4,366,237, UK Patent No. 2,125,570
No., European Patent No. 96,570, West German Patent (Published) No. 3,234,53
Those described in No. 3 are preferred.

Typical examples of polymerized dye-forming couplers include U.S. Patent Nos. 3,451,820, 4,080,211 and 4,367,282.
And British Patent No. 2,102,173.

Couplers that release a photographically useful residue upon coupling can also be preferably used in the present invention. DIR couplers that release development inhibitors are, for example, RD17643, VI described above.
Patents described in paragraphs I to F, JP-A-57-151944, JP-A-57-151944
Preferred are those described in U.S. Pat. Nos. 4,154,962 and US Pat. No. 4,248,962.

Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include, for example, UK Patent No. 2,097,140,
JP-A-2,131,188, JP-A-59-157638, JP-A-59-170840
Those described in the above item are preferred.

Other couplers that can be used in the light-sensitive material of the present invention include, for example, competing couplers described in U.S. Patent No. 4,130,427 and the like, U.S. Patent Nos. 4,283,472 and 4,338,3
No. 93, No. 4,310,618, etc., multi-equivalent couplers described in JP-A-60-185950, DIR redox compounds or DIR coupler releasing couplers described in JP-A-62-24252, etc. or DIR coupler releasing couplers or redox, European Patent 17th
3,302A, etc., which release a dye that recolors after release, such as RD Nos. 11449 and 24241, and JP-A-61-201247.
Bleach accelerator releasing couplers described in, for example, U.S. Pat.
No. 553,477.

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), phosphorus Acid or phosphonic acid esters (e.g., trifel phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate), benzoic acid esters (e.g., 2-ethylhexyl benzoate, dodecyl) Benzoate, 2-ethylhexyl-p-hydroxybenzoate), amides (eg, N, N-diethyldodecaneamide, N, N-diethyllauramide, N-tetradecylpyrrolidone), alcohols or phenol (E.g., isostearyl alcohol, 2,4-di-tert-amylphenol), aliphatic carboxylic acid esters (e.g., bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, tris Octyl citrate), aniline derivatives (eg, N, N
-Dibutyl-2-butoxy-5-tert-octylaniline) and hydrocarbons (for example, paraffin, dodecylbenzene, diisopropylnaphthalene) and the like.
Further, as an auxiliary solvent, the boiling point is about 30 ℃ or more, preferably
An organic solvent having a temperature of 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.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in U.S. Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

The present invention can be applied to various color light-sensitive 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.

When the present invention is used for a color photographing material, the present invention can be applied to photosensitive materials having various structures and photosensitive materials in which a layer structure and a special color material are combined.

A representative example will be described. JP-B-47-49031, JP-B-4
No. 9-3843, JP-B-50-21248, JP-A-59-38147,
JP-A-59-60437, JP-A-60-227256, JP-A-61-4
No. 043, JP-A-61-43743, JP-A-61-42657, etc., in which the coupling speed and diffusion of a color coupler are combined with the layer constitution. JP-B-49-15495, U.S. Pat.No. 3,843,469, in which the same color-sensitive layer is divided into two or more layers, JP-B-53-37017, JP-B-53-37018,
JP-A-51-49027, JP-A-52-143016, JP-A-53-9
No. 7424, JP-A-53-97831, JP-A-62-200350, JP-A-59-177551, the arrangement of the high-sensitivity layer and the low-sensitivity layer and the arrangement of layers having different color sensitivity were defined. And the like.

Suitable supports that can be used in the present invention include, for example, those described above.
From page 28 of RD.No.17643, and from the right column of page 647 of No.18716
It is described in the left column on page 648.

The color photographic light-sensitive material according to the present invention is described in RD.
Developing can be carried out by the usual methods described in 17643, pp. 28-29, and No. 18716, 651, left column to right column.

The color developer used in the development of the photosensitive material of the present invention is
An alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component is preferred. Aminophenol compounds are also useful as the color developing agent.
Phenylenediamine compounds are preferably used, and typical examples thereof are 3-methyl-4-amino-N, N-diethylaniline and 3-methyl-4-amino-N-ethyl-N
-Β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N
-Β-methoxyethylaniline and sulfates, hydrochlorides or p-toluenesulfonates thereof. These compounds can be used in combination of two or more depending on the purpose.

Color developing solutions are pH buffers such as alkali metal carbonates, borates or phosphates, bromide salts, iodide salts,
It generally contains a development inhibitor or an antifoggant such as a benzimidazole, a benzothiazole or a mercapto compound. If necessary, such as hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenylsemicarbazide, triethanolamine, catecholsulfonic acid, and triethylenediamine (1,4-diazabicyclo [2,2,2] octane) Various preservatives, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers,
Fogging agent such as sodium boron hydride, 1
Auxiliary developing seeds such as -phenyl-3-pyrazolidone,
Viscosity imparting agents, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, various chelating agents represented by phosphonocarboxylic acids, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic 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 representative examples.

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

The color developing solution and the black-and-white developing solution generally have a pH of 9 to 12. The replenishment amounts of these developers are
Although it depends on the color photographic light-sensitive material to be processed, it is generally 3 or less per square meter of the light-sensitive material, and can be reduced to 500 ml or less by reducing the bromide ion concentration in the replenisher. 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. Further, the amount of replenishment can 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 between 2 and 5 minutes, but the processing time can be further shortened by using a high temperature, a high pH, and using a high concentration of the color developing agent.

The photographic emulsion tank after color development is usually bleached. 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-fix baths,
Fixing processing before bleach-fixing processing or bleaching processing after bleach-fixing processing can be arbitrarily performed according to the purpose.
Examples of the bleaching agent include iron (III), cobalt (III),
Compounds of polyvalent metals such as chromium (VI) and copper (II), peracids, quinones, nitro compounds and the like are used. Representative bleaches include ferricyanide; dichromate; iron (II
Organic complex salts of I) or cobalt (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3
-Use of aminopolycarboxylic acids such as diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, or complex salts such as citric acid, tartaric acid, and malic acid; persulfates; bromates; permanganates; it can. Among these, iron aminopolycarboxylates (II) including iron (III) complex salts of ethylenediaminetetraacetate
I) Complex salts and persulfates are preferred from the viewpoint of rapid processing and prevention of environmental pollution. In addition, iron (III) aminopolycarboxylate
Complex salts are particularly useful in both bleaching and bleach-fixing solutions. The pH of the bleaching solution or the bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 5.5 to 8, but the processing can be carried out at a lower pH in order to speed up the processing.

A bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their prebaths, if necessary. Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893,858 and the like. Further, the compounds described in U.S. Pat. No. 4,552,834 are also preferable. 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.

Examples of the fixing agent include thiosulfates, thiocyanates, thioether-based compounds, thioureas, and a large amount of iodide.The use of thiosulfates is common,
In particular, ammonium thiosulfate can be used most widely. As a preservative of the bleach-fixing solution, a sulfite, a bisulfite or a carbonyl bisulfite adduct is preferable.

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, depending on the material used, such as a coupler), the application, the rinsing water temperature,
It can be set in a wide range depending on the number of washing tanks (number of stages), a replenishment method such as countercurrent flow, forward flow, and other various conditions. 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 of Motion Picture and
It can be determined by the method described in Television Engineers, Vol. 64, pp. 248-253 (May, 1955).

According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced.However, due to an increase in the residence time of water in the tank, bacteria are propagated, and the generated suspended matter adheres to the photosensitive material. Problem arises. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, calcium ion described in Japanese Patent Application No. 61-131,632,
The method of reducing magnesium ions can be used very effectively. Also, isothiazolone compounds and thiabendazoles described in JP-A-57-8542, chlorine-based disinfectants such as chlorinated sodium isocyanurate, polybenzotriazoles, etc. And the fungicides described in "Sterilization, Sterilization, and Fungicide Technology for Microorganisms" edited by the Sanitary Technology Society, and "Encyclopedia of Fungicides and Fungicides" edited by the Japan Society of Antifungals and Fungi.

In the processing of the photosensitive material of the present invention, the pH of the washing water is 4-
9, preferably 5-8. Washing water salt, washing time can also be set variously depending on the characteristics of the photosensitive material, the use, etc.
A range of 30 seconds-5 minutes is selected. Further, the light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the above-mentioned washing. In such a stabilization process, Japanese Unexamined Patent Application Publication No.
Known methods described in JP-A-57-8,543, JP-A-58-14,834, and JP-A-60-220,345 can all be used.

In some cases, a stabilization process may be performed after the water washing process. For example, the stabilization process is used as a final bath of a color photographic material for photography. Examples include a stabilizing bath containing formalin and a surfactant. Various chelating agents and fungicides can also be added to this stabilizing bath.

The overflow solution resulting from the washing and / or replenishment of the stabilizing solution can be reused in another step such as a desilvering step.

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.

The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-
3-pyrazolidones may be incorporated. Typical compounds are described in JP-A-56-64,339, JP-A-57-144,547, and JP-A-58-144,547.
No. 115,438 and the like.

The various processing solutions in the present invention are used at 10 ° C to 50 ° 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 conversely, lowers the temperature to achieve the improvement of the image quality and the stability of the processing solution. be able to. Further, in order to save silver of the light-sensitive material, a process using cobalt intensification or hydrogen peroxide intensification described in West German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be performed.

The silver halide light-sensitive material of the present invention is disclosed in U.S. Pat.
No. 500,626, JP-A-60-133449, JP-A-59-218443, JP-A-6
It is also applicable to the photothermographic materials described in 1-238056, European Patent 210,660A2, and the like.

 An example will be described below.

Example 1. Average iodine content is 20 mol%, average sphere equivalent diameter 0.8 μm,
A silver iodobromide double twin crystal grain having a coefficient of variation of 19% and an average aspect ratio of 5.0 is used as a seed crystal, and the silver potential is set to −40 mV in an aqueous solution of gelatin. I attached it. The ratio of the core to the shell was adjusted to 1: 2 in terms of the silver amount ratio, and the composition of the halogen solution was controlled so that the iodine content of the shell was 0 mol% to 7.5 mol% in the formulation. (Prescriptions A to E shown in Table 1) During the formation of the shell, reduction sensitization was performed according to the amount and method of addition of dimethylamine borane (DMAB) and a thiosulfonic acid compound shown in Table 2.

After grain formation, the emulsion is subjected to a normal desalinated water washing step at 40 ° C.
It was redispersed under the conditions of pAg8.9 and pH6.3. Each emulsion is then
Each was optimally chemically sensitized using 6 × 10 ^-6 mol of sodium thiosulfate and 2 × 10 ^-6 mol of chloroauric acid per mol of silver halide. An emulsion to which a spectral sensitizing dye having the following structural formula was added prior to chemical sensitization was prepared. Dyes A and B were each added to 1 mol of silver halide in the emulsion.
2.5 × 10 ^-4 mol and 3.0 × 10 ^-4 mol were added.

The emulsion and the protective layer were coated on the triacetyl cellulose film support provided with the undercoat layer in the coating amounts shown in Table 3.

Table 3 (1) Emulsion layer-Emulsion: Emulsions shown in Table 4 (silver 1.7 × 10 ^-2 mol / m ² )-Coupler (1.5 × 10 ^-3 mol / m ² ) ・ Tricresyl phosphate (1.10 g / m ² ) ・ Gelatin (2.30 g / m ² ) (2) Protective layer ・ 2,4-Dichlorotriazine-6-hydroxy-s-
Triazine sodium salt (0.08 g / m ² ) and gelatin (1.80 g / m ² ) These samples were exposed to sensitometric exposure and subjected to the following color development processing.

The density of the treated sample was measured with a green filter. Table 4 shows the obtained photographic performance results.

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

1. Color development ... 2 minutes 45 seconds 2. Bleaching ... 6 minutes 30 seconds 3. Rinse ... 3 minutes 15 seconds 4. Settle down ... 6 minutes 30 seconds 5. Rinse ... 3 minutes 15 seconds 6. Stable: 3 minutes 15 seconds The treatment composition used for each process is as follows.

Color developer Sodium nitrilotriacetate 1.4 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 Water 1 Bleaching solution 1 Bleaching solution Ammonium bromide 160.0 g Ammonia water (28% w / w) 25.0 ml Ethylenediamine-ferric sodium ferric sodium trihydrate 130
g Glacial acetic acid 14 ml Add water 1 Fixer Sodium tetrapolyphosphate 2.0 g Sodium sulfite 4.0 g Ammonium thiosulfate (700 g /) 175.0 ml Sodium bisulfite 4.6 g Add water 1 Stabilizer Formalin 8.0 ml Add water 1 Exposure was carried out by ordinary wedge exposure for 1 second and 1/100 second.

A light source adjusted to a color temperature of 4800 ° K using a filter was used, and a blue filter (BPN42, manufactured by Fuji Photo Film Co., Ltd.) or a yellow filter was used. The sensitivity was compared at a point of 0.2 in optical density from fog. The sensitivity is indicated by the blue sensitivity of the sample using Emulsion 1.
The relative speed was expressed as 100, with the minus blue speed of Emulsions 2 and 3 as 100. Table 4 shows the results for the samples with an exposure time of 1/100 second.

For example, emulsions Nos. 2 and 9 are emulsions which are not subjected to reduction sensitization and use dye A as a spectral sensitizing dye, so that the effect of the surface silver iodide content when reduction sensitization is not performed can be seen. . When the mol% of the surface Ag I was changed from 2.5 to 7.5 mol%, both the blue sensitivity and the minus blue sensitivity decreased.

However, for example, the relationship between Emulsions Nos. 5 and 12 is that the dye A was used as the spectral sensitizing dye in the emulsion subjected to reduction sensitization,
In the case of reduction sensitization, it is apparent that the blue sensitivity and the minus blue sensitivity corresponding to the change of 2.5 to 7.5 mol% of the surface AgI also increase.

Example 2 The following dyes were added to the chemically sensitized emulsions 1, 4, 8, and 11 prepared in Example 1 to prepare red-, green-, and blue-sensitive emulsions.

Dye Group 3 (Blue Sensitive Dye) Sensitizing Dye VIII 2.2 × 10 ^-4 mol / mol Ag On each cellulose triacetate film support undercoated with these emulsions, each layer having the following composition is superposed. By coating, Sample 201 which is a multilayer color photosensitive material was produced.

(Composition of photosensitive layer) The number corresponding to each component indicates the coating amount expressed 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 201) First layer: Antihalation layer Black colloidal silver: silver 0.18 Gelatin: 1.40 Second layer: intermediate layer 2.5-di-t-pentadecylhydroquinone: 0.18 EX-1: 0.07 EX-3 ・ ・ ・ 0.02 EX-12 ・ ・ ・ 0.002 U-1 ・ ・ ・ 0.06 U-2 ・ ・ ・ 0.08 U-3 ・ ・ ・ 0.10 HBS-1 ・ ・ ・ 0.10 HBS-2 ・ ・ ・ 0.02 Gelatin ... 1.04 Third layer (first red-sensitive emulsion layer) Monodispersed silver iodobromide emulsion (silver iodide 6 mol%, average grain size 0.1%)
6 μ, coefficient of variation related to particle size 0.15) Silver 0.55 Sensitizing dye I 6.9 × 10 ^-5 Sensitizing dye II 1.8 × 10 ^-5 Sensitizing dye III 3.1 × 10 ^-4 Sensitizing dye IV ・ ・ ・ 4.0 × 10 ^-5 EX-2 ・ ・ ・ 0.350 HBS-1 ・ ・ ・ 0.005 EX-10 ・ ・ ・ 0.020 Gelatin ・ ・ ・ 1.20 Fourth layer (second red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 10 mol%, average grain size 0.
7μ, average aspect ratio 5.5, average thickness 0.2μ) ・ ・ ・ Silver
1.0 Sensitizing dye I ・ ・ ・ 5.1 × 10 ^-5 Sensitizing dye II ・ ・ ・ 1.4 × 10 ^-5 Sensitizing dye III ・ ・ ・ 2.3 × 10 ^-4 Sensitizing dye IV ・ ・ ・ 3.0 × 10 ^-5 EX -2: 0.400 EX-3: 0.050 EX-10: 0.015 Gelatin: 1.30 Fifth layer (third red-sensitive emulsion layer) Silver iodobromide emulsion I: Silver 1.60 EX-3・ ・ ・ 0.240 EX-4 ・ ・ ・ 0.120 HBS-1 ・ ・ ・ 0.22 HBS-2 ・ ・ ・ 0.10 Gelatin ・ ・ ・ 1.63 6th layer (intermediate layer) EX-5 ・ ・ ・ 0.040 HBS-1 ・ ・ ・0.020 gelatin ・ ・ ・ 0.80 7th layer (first green-sensitive emulsion layer) Tabular silver iodobromide emulsion (silver iodide 6 mol%, average grain size of 0,0)
6μ, average aspect ratio 6.0, average thickness 0.15) ・ ・ ・ Silver 0.
40 Sensitizing dye V ・ ・ ・ 3.0 × 10 ^-5 Sensitizing dye VI ・ ・ ・ 1.0 × 10 ^-4 Sensitizing dye VII ・ ・ ・ 3.8 × 10 ^-4 EX-6 ・ ・ ・ 0.260 EX-1 ・ ・ ・0.021 EX-7 0.030 EX-8 0.025 HBS-1 0.100 HBS-4 0.010 Gelatin 0.75 Eighth layer (second green-sensitive emulsion layer) Monodisperse iodine bromide Silver emulsion (9 mol% of silver iodide, average grain size of 0.
7 μ, coefficient of variation with respect to particle size 0.18) Silver 0.80 Sensitizing dye V 2.1 × 10 ^-5 Sensitizing dye VI 7.0 × 10 ^-5 Sensitizing dye VII 2.6 × 10 ^-4 EX-6 ・ ・ ・ 0.180 EX-8 ・ ・ ・ 0.010 EX-1 ・ ・ ・ 0.008 EX-7 ・ ・ ・ 0.012 HBS-1 ・ ・ ・ 0.160 HBS-4 ・ ・ ・ 0.008 Gelatin ・ ・ ・ 1.10 9th layer (Third green-sensitive emulsion layer) Silver iodobromide emulsion II ... silver 1.2 EX-6 ... 0.065 EX-11 ... 0.030 EX-1 ... 0.025 HBS-1 ... 0.25 HBS-2・ ・ ・ 0.10 gelatin ・ ・ ・ 1.74 10th layer (yellow filter layer) yellow colloidal silver ・ ・ ・ silver 0.05 EX-5 ・ ・ ・ 0.08 HBS-3 0.03 gelatin ・ ・ ・ 0.95 11th layer (first blue-sensitive emulsion Layer) Tabular silver iodobromide emulsion (silver iodide 6 mol%, average grain size 0.1%)
6μ, average aspect ratio 5.7, average thickness 0.15) ・ ・ ・ Silver 0.
24 Sensitizing dye VIII ・ ・ ・ 3.5 × 10 ^-4 EX-9 ・ ・ ・ 0.85 EX-8 ・ ・ ・ 0.12 HBS-1 ・ ・ ・ 0.28 Gelatin ・ ・ ・ 1.28 12th layer (2nd blue-sensitive emulsion layer) Monodispersed silver iodobromide emulsion (silver iodide 10 mol%,
8μ, coefficient of variation related to particle size 0.16) ・ ・ ・ Silver 0.45 Sensitizing dye VIII ・ ・ ・ 2.1 × 10 ^-4 EX-9 ・ ・ ・ 0.20 EX-10 ・ ・ ・ 0.015 HBS-1 ・ ・ ・ 0.03 Gelatin・ 0.46 thirteenth layer (third blue-sensitive emulsion layer) Silver iodobromide emulsion III ・ ・ ・ silver 0.77 EX-9 ・ ・ ・ 0.20 HBS-1 ・ ・ ・ 0.07 gelatin ・ ・ ・ 0.69 14th layer (first protection) Layer) Silver iodobromide emulsion (silver iodide 1 mol%, average grain size 0.07μ)
・ ・ ・ Silver 0.5 U-4 ・ ・ ・ 0.11 U-5 ・ ・ ・ 0.17 HBS-1 ・ ・ ・ 0.90 Gelatin ・ ・ ・ 1.00 15th layer (2nd protective layer) Polymethyl acrylate particles (about 1.5 μm in diameter) ...
0.54 S-1 ... 0.15 S-2 ... 0.05 Gelatin ... 0.72 In addition to the above components, gelatin hardener H-1 and a surfactant were added to each layer. The structural formula of the compound used is represented by
It is shown in the table.

Silver iodobromide emulsion I of the fifth layer, silver iodobromide emulsion of the ninth layer
II, except that the silver iodobromide emulsion III of the 13th layer was changed.
Samples 202 to 204 were produced in the same manner as in 01.

These samples were subjected to sensitometric exposure and subjected to the following color development processing.

The concentration of the treated sample was measured using a red filter, a green filter, and a blue filter. Table 5 shows the obtained results.

The results of the photographic performance were described as relative sensitivities when the sensitivity of the sample 201 was 100, where the sensitivities of the red-sensitive layer, the green-sensitive layer, and the blue-sensitive layer were each 100.

Processing Method Color development was carried out at 38 ° C. according to the following processing steps.

Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Rinse 2 minutes 10 seconds Fixed 4 minutes 20 seconds Rinse 3 minutes 15 seconds Stable 1 minute 05 seconds The processing liquid composition used in each process is as follows. Was.

Color developing solution Diethylenetriaminepentaacetic acid 1.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 g Sodium sulfite 4.0 g Potassium carbonate 30.0 g Potassium bromide 1.4 g Potassium iodide 1.3 mg Hydroxylamine sulfate 2.4 g 4- (N- Ethyl-N-β-hydroxyethylamino)
-2-Methylaniline sulfate 4.5 g Add water 1.0 pH 10.0 Bleaching solution Ferric ammonium ethylenediaminetetraacetate 100.0 g Disodium ethylenediaminetetraacetate 10.0 g Ammonium bromide 150.0 g Ammonium nitrate 10.0 g Add water 1.0 pH6 .0 Fixer Ethylenediaminetetraacetic acid disodium salt 1.0 g Sodium sulfite 4.0 g Ammonium thiosulfate aqueous solution (70%) 175.0 ml Sodium bisulfite 4.6 g Add water 1.0 pH 6.6 Stabilizer Formalin (40%) 2.0 ml Polyoxyethylene p-Monononyl phenyl ether (average degree of polymerization: 10) 0.3 g with addition of water 1.0 As is clear from Table 5, the emulsion of the present invention hardly increases fog and has an effect of sensitization.

Example 3 The average iodine content was 20 mol%, the average sphere equivalent diameter was 0.9 μm,
A silver iodobromide double twin crystal grain having a coefficient of variation of 19% and an average aspect ratio of 5.0 is used as a seed crystal, and the silver potential is set to −40 mV in an aqueous solution of gelatin. I attached it. The ratio of the core and the shell was adjusted to 1: 2 in terms of the silver amount ratio, and the composition of the halogen solution was controlled so that the iodine content of the shell was 0 mol% to 5.0 mol% in the formulation.

One minute after the start of shell formation, L-ascorbic acid or L-ascorbic acid and thiosulfonic acid compound 1-2
Was added. Stannous chloride and thiourea dioxide were also added as comparative reducing agents.

 Table 6 summarizes the contents of the emulsions 31 to 40.

After grain formation, the emulsion is subjected to a normal desalinated water washing step at 40 ° C.
It was redispersed under the conditions of pAg8.9 and pH6.3. Each emulsion is then
Each was optimally chemically sensitized using 6 × 10 ^-6 mol of sodium thiosulfate and 2 × 10 ^-6 mol of chloroauric acid per mol of silver halide. Prior to chemical sensitization, a spectral sensitizing dye having the following structural formula was added in an amount of 2.5 × 10 ^-4 per mol of silver halide.
And an emulsion to which 3.0 × 10 ⁻⁴ mol was added.

The emulsion and the protective layer were coated at the coating amounts shown in Table 7 on a triacetyl cellulose film support provided with an undercoat layer.

Table 7 (1) Emulsion layer ・ Emulsion: Emulsions shown in Tables 8 and 9 (silver 1.7 × 10 ^-2 mol / m ² ) ・ Coupler (1.5 × 10 ^-3 mol / m ² ) ・ Tricresyl phosphate (1.10 g / m ² ) ・ Gelatin (2.30 g / m ² ) (2) Protective layer ・ 2,4-Dichlorotriazine-6-hydroxy-s-
Triazine sodium salt (0.08 g / m ² ) and gelatin (1.80 g / m ² ) These samples were exposed to sensitometric exposure as described below, and were subjected to the following color development processing.

 The density of the treated sample was measured with a green filter.

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

1. Color development ... 2 minutes 45 seconds 2. Bleaching ... 6 minutes 30 seconds 3. Rinse ... 3 minutes 15 seconds 4. Settle down ... 6 minutes 30 seconds 5. Rinse ... 3 minutes 15 seconds 6. Stable: 3 minutes 15 seconds The treatment composition used for each process is as follows.

Color developer Sodium nitrilotriacetate 1.4 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 Water 1 Bleaching solution 1 Bleaching solution Ammonium bromide 160.0 g Ammonia water (28% w / w) 25.0 ml Ethylenediamine-ferric sodium ferric sodium trihydrate 130
g Glacial acetic acid 14 ml Add water 1 Fixer Sodium tetrapolyphosphate 2.0 g Sodium sulfite 4.0 g Ammonium thiosulfate (700 g /) 175.0 ml Sodium bisulfite 4.6 g Add water 1 Stabilizer Formalin 8.0 ml Add water 1 Table 8 shows the photographic properties of the samples chemically sensitized by adding spectral sensitizing dye A to emulsions 31 to 40. Exposure was performed for 1/100 second through a yellow filter. The sensitivity was evaluated at a density of fog +0.2. Table 8 shows the photographic properties immediately after the coating and the photographic properties after the sample was allowed to stand for 2 months in an atmosphere at 23 ° C. and a relative humidity of 55%.

Table 9 shows the photographic characteristics of the samples sensitized by using the emulsions 31, 32, 35, and 40 of Table 6 without using the spectral sensitizing dye and chemically sensitized by adding the spectral sensitizing dye B. . Samples without spectral sensitizing dye were passed through a blue filter while dye B
1/100 through the yellow filter
Exposure was performed in seconds. The sensitivity was evaluated at a density of fog +0.2.

From Table 8, it can be seen that the emulsion sensitized by reduction with L-ascorbic acid was 5.7 mol% (emulsion-34) and 7.5 mol% as compared with the emulsion having a surface iodine content of 2.5 mol% by XPS (emulsion-32).
It can be seen that higher sensitivity can be achieved in the case of (Emulsion-40). Similarly, Table 9 shows that the combination of the surface iodine content and the reduction sensitization using L-ascorbic acid gives preferable results. From the comparison of emulsions 39 and 40, L-
It can be seen that the use of a combination of ascorbic acid and thiosulfonic acid gives more favorable results. Emulsions 37, 38 and 40
From the comparison of the above, reduction sensitization using L-ascorbic acid not only gives a more favorable result than the case where other reducing agents are used, but also shows an increase in fog and a decrease in sensitivity caused when the coated sample is aged over time. It can be seen that it has a favorable property of being very small.

Example 4 Dyes were added to the chemically sensitized emulsions 32, 35, 38, and 40 prepared in Example 3 to prepare red-, green-, and blue-sensitive emulsions.

Samples 301 to 304, which are multilayer color photographic materials, were prepared by coating each layer having the following composition on a cellulose triacetate film support undercoated with these emulsions.

(Composition of photosensitive layer) The coating amount is a number in g / m ² . However, for silver halide and colloidal silver, the amount expressed in g / m ^{2 of} silver is
The sensitizing dyes are shown in terms of moles per mole of silver halide in the same layer.

First layer: Antihalation layer Black colloidal silver Silver coating amount 0.2 Gelatin 2.2 UV-1 0.1 UV-2 0.2 Cpd-1 0.05 Solv-1 0.01 Solv-2 0.01 Solv-3 0.08 Second layer: Intermediate layer Fine particle silver bromide (Sphere equivalent diameter 0.07μ) Silver coating amount
0.15 Gelatin 1.0 ExC-4 0.03 Cpd-2 0.2 Third layer: First red-sensitive emulsion layer Silver iodobromide emulsion (Ag I 8.5 mol%, internal high Ag I type, equivalent sphere diameter 0.1 μm, equivalent sphere diameter Coefficient of variation 25%, diameter / thickness ratio 3.0)
Silver coating amount 0.42 Silver iodobromide emulsion (Ag I 4.0mol%, internal high Ag I type, equivalent spherical diameter 0.4μ, variation coefficient of equivalent spherical diameter 22%, tetradecahedral particles) Silver coating amount 0.33 Gelatin 1.0 ExS- 1 4.5 × 10 ^-4 mol ExS-2 1.5 × 10 ^-4 mol ExS-3 0.4 × 10 ^-4 mol ExC-1 0.40 ExC-2 0.11 ExC-3 0.009 ExC-4 0.023 Solv-1 0.24 4th layer: 2 Red-sensitive emulsion layer Silver iodobromide emulsion (Ag I 8.5 mol%, internal high Ag I type, sphere equivalent diameter 1.0 μ, coefficient of variation of sphere equivalent diameter 25%, plate-like grains, diameter /
Thickness ratio 3.0) Silver coating amount 0.55 Gelatin 0.7 ExS-1 3 × 10 ^-4 ExS-2 1 × 10 ^-4 ExS-3 0.3 × 10 ^-4 ExC-1 0.10 ExC-2 0.55 ExC-4 0.025 Solv-1 0.20 Fifth layer: Third red-sensitive emulsion layer Silver iodobromide emulsion I (Ag I 11.3 mol%, internal high Ag I type, equivalent spherical diameter 1.4 µ, coefficient of variation of equivalent spherical diameter 28%, plate-like grains, diameter / Thickness ratio 6.0) Silver coating amount 1.29 Gelatin 0.6 ExS-1 2 × 10 ^-4 ExS-2 0.6 × 10 ^-4 ExS-3 0.2 × 10 ^-4 ExC-2 0.08 ExC-4 0.01 ExC-5 0.06 Solv-1 0.12 Solv-2 0.12 6th layer: Intermediate layer Gelatin 1.0 Cpd-4 0.1 Solv-1 0.1 7th layer: First green-sensitive emulsion layer Silver iodobromide emulsion (Ag I 8.5 mol%, internal high Ag I type, Equivalent sphere diameter 1.0μ, Coefficient of variation of sphere equivalent diameter 25%,
Thickness ratio 3.0) Silver coating amount 0.28 Silver iodobromide emulsion (Ag I 14.0 mol%, internal high Ag I type, sphere equivalent diameter 0.7μ, sphere equivalent diameter variation coefficient 38%, plate-like grains, diameter /
Thickness ratio 2.0) Silver coating amount 0.1 Gelatin 1.2 ExS-5 5 × 10 ^-4 ExS-6 2 × 10 ^-4 ExS-7 1 × 10 ^-4 ExM-1 0.50 ExM-2 0.10 ExM-5 0.03 Solv-1 0.2 Solv-4 0.03 Eighth layer: Second green-sensitive emulsion layer Silver iodobromide emulsion (Ag I 8.5 mol%, internal high iodine type, equivalent spherical diameter 1.0 μ, equivalent coefficient of equivalent spherical diameter 25%, tabular grain , Diameter / thickness ratio 3.0) Silver coating amount 0.47 Gelatin 0.35 ExS-5 3.5 × 10 ^-4 ExS-6 1.4 × 10 ^-4 ExS-7 0.7 × 10 ^-4 ExM-1 0.12 ExM-2 0.01 ExM-3 0.01 Solv-1 0.15 Solv-4 0.03 Ninth layer: Intermediate layer Gelatin 0.5 Tenth layer: Third green-sensitive emulsion layer Silver iodobromide emulsion II (Ag I 11.3 mol%, internal high Ag I type, equivalent sphere diameter 1.4) μ, coefficient of variation of equivalent sphere diameter 28%, plate-like particles, diameter / thickness ratio 6.0) Silver coating amount 1.3 Gelatin 0.8 ExS-5 2 × 10 ^-4 ExS-6 0.8 × 10 ^-4 ExS-7 0.8 × 10 ^{-4 ExM-3 0.01 ExM-4} 0.04 ExC-4 0.005 Cpd-5 0.01 Solv-1 0.2 11th layer: yellow filter Cpd-3 0.05 Gelatin 0.5 Solv-1 0.1 12th layer: Intermediate layer Gelatin 0.5 Cpd-2 0.1 13th layer: 1st blue-sensitive emulsion layer Silver iodobromide emulsion (Ag I10 mol%, internal high iodine type, equivalent to sphere) 0.7μ diameter, coefficient of variation of equivalent sphere diameter 14%, tetrahedral grains) Silver coating amount 0.1 Silver iodobromide emulsion (Ag I 4.0mol%, internal high iodine type, equivalent sphere diameter 0.4μ, variation of equivalent sphere diameter) Silver coating amount 0.05 Gelatin 1.0 ExS-8 3 × 10 ^-4 ExY-1 0.60 ExY-2 0.02 Solv-1 0.15 14th layer: 2nd blue-sensitive emulsion layer Silver iodobromide emulsion Ag I9.0mol%, internal high Ag I type, equivalent sphere diameter 1.0μ, coefficient of variation of equivalent sphere diameter 16%, tetrahedral particles) Silver coating 0.19 gelatin 0.3 ExS-8 2 × 10 ^-4 ExY-1 0.22 Solv-1 0.07 15th layer: Intermediate layer Fine grain silver iodobromide (Ag I2 mol%, uniform type, equivalent sphere diameter 0.13
μ) Silver coating amount 0.2 Gelatin 0.36 16th layer: 3rd blue-sensitive emulsion layer Silver iodobromide emulsion III (Ag I 11.3 mol%, internal high Ag I type, equivalent spherical diameter 1.4μ, coefficient of variation of equivalent spherical diameter 28%, plate-like particles, diameter / thickness ratio 6.0) Silver coating amount 1.35 Gelatin 0.5 ExS-9 1.5 × 10 ^-4 ExY-1 0.2 Solv-1 0.07 17th layer: 1st protective layer Gelatin 1.8 UV-1 0.1 UV -2 0.2 Solv-1 0.01 Solv-2 0.01 18th layer: 2nd protective layer Fine silver chloride (equivalent sphere diameter 0.07μ) Silver coating amount
0.36 Gelatin 0.70 Polymethyl methacrylate particles (1.5 μm in diameter) 0.2 W-1 0.02 H-1 0.4 Cpd-6 1.0 The chemical structural formulas of the compounds used to prepare Samples 301 to 304 are shown in Table C below.

These samples were subjected to sensitometric exposure and subjected to the following color development processing.

The concentration of the sample of the treatment agent was measured with a red filter, a green filter, and a blue filter. Table 10 shows the obtained results.

The results of the photographic performance were described as relative sensitivities when the sensitivity of the red-sensitive layer, the green-sensitive layer, and the blue-sensitive layer was 100 when the sensitivity of the sample 302 was 100.

Processing Method Color development was carried out at 38 ° C. according to the following processing steps.

Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Rinse 2 minutes 10 seconds Fixed 4 minutes 20 seconds Rinse 3 minutes 15 seconds Stable 1 minute 05 seconds The processing liquid composition used in each process is as follows. Was.

Color developing solution Diethylenetriaminepentaacetic acid 1.0 g 1-hydroxyethylidene-1,1-diphosphone 2.0 g Sodium sulfite 4.0 g Potassium carbonate 30.0 g Potassium bromide 1.4 g Potassium iodide 1.3 mg Hydroxylamine sulfate 2.4 g 4- (N-ethyl -N-βhydroxyethylamino)-
2-Methylaniline sulfate 4.5 g Add water 1.0 pH 10.0 Bleach solution Ferric ammonium ethylenediaminetetraacetate 100.0 g Disodium ethylenediaminetetraacetate 10.0 g Ammonium bromide 150.0 g Ammonium nitrate 10.0 g Add water 1.0 pH 6.0 Fixer Ethylenediaminetetraacetic acid disodium salt 1.0 g Sodium sulfite 4.0 g Ammonium thiosulfate aqueous solution (70%) 175.0 ml Sodium bisulfite 4.6 g Add water 1.0 pH 6.6 Stabilizer Formalin (40%) 2.0 ml Polyoxyethylene-p- Monononyl phenyl ether (average degree of polymerization: 10) 0.3 g with water added 1.0 As is clear from Table 10, the emulsion of the present invention hardly increases fog and has a high sensitizing effect.

Samples 303 and 304 were allowed to stand in an atmosphere of 23 ° C. and a relative humidity of 55% for 2 months, and then subjected to sensitometric exposure and color development. For 303, the red, green and blue layers showed a decrease in sensitivity with increasing fog, but 304 did not change.

(Effect) Conventionally, it has been difficult to achieve an increase in sensitivity due to reduction sensitization in a color sensitized emulsion. The present inventors set the surface silver iodide content to 5%.
It has been found that reduction sensitization in silver halide grains of up to 30 mol% can specifically increase the sensitivity of the color sensitized region. For example, if the silver halide grains having a double structure are not subjected to reduction sensitization during grain growth, an increase in the silver iodide content of the shell portion results in a decrease in sensitivity in the color sensitized region.

Another effect that cannot be predicted is that the photographic material of the present invention is hardly deteriorated by natural radiation.

Table A (1-1) CH ₃ SO ₂ SNa (1-2) C ₂ H ₅ SO ₂ SNa (1-3) C ₃ H ₇ SO ₂ SK (1-4) C ₄ H ₉ SO ₂ SLi ( 1-5) C ₆ H ₁₃ SO ₂ SNa (1-6) C ₈ H ₁₇ SO ₂ SNa _{(1-8) C 10 H 21 SO} 2 SNa (1-9) C 12 H 25 SO 2 SNa (1-10) C 16 H 33 SO 2 SNa _{(1-12) t-C 4 H} 9 SO 2 SNa (1-13) CH 3 OCH 2 CH 2 SO 2 S · Na (1-15) CH ₂ = CHCH ₂ SO ₂ SNa (1-29) KSSO ₂ (CH ₂ ) ₂ SO ₂ SK (1-30) NaSSO ₂ (CH ₂ ) ₄ SO ₂ SNa (1-31) NaSSO ₂ (CH ₂ ) ₄ S (CH ₂ ) ₄ SO ₂ SNa (2-1) C ₂ H ₅ SO ₂ S-CH ₃ (2-2) C ₈ H ₁₇ SO ₂ SCH ₂ CH ₃ (2-5) C ₂ H ₅ SO ₂ SCH ₂ CH ₂ CN (2-18) C ₂ H ₅ SO ₂ SCH ₂ CH ₂ CH ₂ CH ₂ OH (2-21) CH ₃ SSO ₂ (CH ₂ ) ₄ SO ₂ SCH ₃ (2-22) CH ₃ SSO ₂ (CH ₂ ) ₂ SO ₂ SCH ₃ (3-2) C ₂ H ₅ SO ₂ SCH ₂ CH ₂ SO ₂ CH ₂ CH ₂ SSO ₂ C ₂ H ₅ (3-7) C ₂ H ₅ SO ₂ SSSO ₂ C ₂ H ₅ (3-8) (n) C ₃ H ₇ SO ₂ SSSO ₂ C ₃ H ₇ (n) Table B HBS-1 Tricresyl phosphate HBS-2 Dibutyl phthalate HBS-3 Bis (2-ethylhexyl) phthalate Table C

Claims (6)

(57) [Claims] An iodide having a grain surface of 5 mol% or more, which has been subjected to reduction sensitization during grain growth and subjected to at least one of gold sensitization, sulfur sensitization and noble metal sensitization in an optional step. A silver halide photographic material having at least one silver halide emulsion layer containing silver halide grains containing silver on a support. 2. The silver halide photographic material according to claim 1, which has been reduction-sensitized in the presence of at least one compound represented by formula [I], [II] or [III]. [I] R-SO ₂ S-M [II] R-SO ₂ S-R ¹ [III] RSO ₂ S-Lm-SSO ₂ -R ^{2 In the} formula, R, R ¹ and R ² may be the same or different. And represents an aliphatic group, an aromatic group, or a heterocyclic group, and M represents a cation. L represents a divalent linking group, and m is 0 or 1. The compounds of the general formulas [I] to [III] may be polymers containing, as a repeating unit, a divalent group derived from the structure represented by any of [I] to [II]. When possible, R, R ¹ , R ² , and L may combine with each other to form a ring. 3. The silver halide photographic light-sensitive material according to claim 1, which contains silver halide grains sensitized by gold and sulfur after reduction sensitization. 4. The silver halide photographic material according to claim 1, which has been reduction-sensitized with at least one of ascorbic acid or a derivative thereof. 5. The method according to claim 4, wherein the silver halide grains are subjected to reduction sensitization with 5 × 10 ^-5 mol to 1 × 10 ^-1 mol of ascorbic acid or a derivative thereof per mol of silver halide. Silver halide photographic material. 6. The silver halide photograph according to claim 4, wherein the reduction sensitization has been carried out in the presence of at least one compound represented by the general formula [I], [II] or [III]. Photosensitive material. [I] R-SO ₂ S-M [II] R-SO ₂ S-R ¹ [III] R-SO ₂ S-Lm-SSO ₂ -R ^{2 In the} formula, even if R, R ¹ and R ² are the same, It may be different and represents an aliphatic group, an aromatic group, or a heterocyclic group, and M represents a cation. L represents a divalent linking group, and m is 0 or 1. The compounds of the general formulas [I] to [III] may be polymers containing, as a repeating unit, a divalent group derived from the structure represented by any of [I] to [II].