JPH02189541A - Production of silver halide emulsion - Google Patents

Abstract

PURPOSE:To obtain the photosensitive material which has high sensitivity and fogs less by subjecting the silver halide emulsion to reduction sensitization by at least one kind of ascorbic acid or the derivatives thereof. CONSTITUTION:The silver halide emulsion is subjected to the reduction sensitiza tion by at least one kind of the ascorbic acid or the derivatives thereof in the production process for the silver halide emulsion. The emulsion is chemically sensitized in the presence of a spectral sensitizing dyestuff at the time of the chemical sensitization thereof. The emulsion which has the high sensitivity and excellent graininess, the color sensitizing emulsion which has the high sensitivity and fogs less and further the color sensitizing emulsion which has the high sensitivity and an excellent preservable property are obtd. in this way. In addition, the photographic sensitive material which has the high sensitiv ity and excellent graininess, the photographic sensitive material which has the high sensitivity and fogs less and the photographic sensitive material which has the high sensitivity and an excellent preservable property are obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a silver halide photographic emulsion that provides a light-sensitive material with high sensitivity and little fog.

The present invention also relates to a method for producing a silver halide photographic emulsion that provides a light-sensitive material with little variation in sensitivity and fog during storage of the light-sensitive material.

[Prior art]

The basic properties required of silver halide emulsions for photography are high sensitivity, low fog, and fine grain.

In order to increase the sensitivity of an emulsion, (1) increase the number of photons absorbed by a single grain; (2) increase the efficiency with which photoelectrons generated by light absorption are converted into silver clusters (latent images); and (3) it is necessary to increase the development activity in order to effectively utilize the formed latent image.

Increasing the size increases the number of photons absorbed by one particle, but
Decrease image quality. Increasing development activity is also an effective means to increase sensitivity, but in the case of parallel development such as color development, sensitivity is generally increased without causing graininess deterioration. It is most desirable to increase the efficiency of converting photoelectrons into latent images, that is, to increase quantum sensitivity. In order to increase quantum sensitivity, it is necessary to eliminate inefficient processes such as recombination and latent image dispersion as much as possible. It is known that a reduction sensitization method in which small sl nuclei with no development activity are created inside or on the surface of silver halide is effective in preventing recombination.

Attempts at reduction sensitization have been considered for a long time.

Carroll, U.S. Patent No. 2,487,
No. 850, tin compounds, Lowe et al. No. 2,512,925, polyamine compounds, Fattens et al.
No. 89.823 discloses that thiourea dioxide-based compounds can be used as reduction sensitizers. Furthermore, Co
11ier (Korea) is PhotographicS
science and engineering 23
Volume 113 (1979) compares the properties of silver nuclei produced by various reduction sensitization methods. She employed dimethylamine borane, stannous chloride, hydrazine, high pH aging, and low pAg aging.

The method of reduction sensitization is further described in U.S. Pat. No. 2,518°698.
No. 3.201,254, No. 3.411.91
No. 7, No. 3,779,777, No. 3,930,8
It is also disclosed in No. 67.

Japanese Patent Publication No. 57-33572 and No. 58-1410 discuss not only the selection of reduction sensitizers but also the improvement of reduction aggravation methods. Among these, conventionally known reduction sensitizers are listed, and ascorbic acid is mentioned among them. However, compounds such as thiourea dioxide are preferred, and those shown in the Examples are thiourea dioxide, silver ripening, and hydrazine. Therefore, favorable properties of ascorbic acid compounds as reduction sensitizers have not been found. Regarding further ingenuity, JP-A-57=179
No. 835.

However, in order to put reduction sensitization into practical use, it is necessary to overcome the problem of the storage stability of light-sensitive materials.There is also a technique for improving the storage stability of reduction-sensitized emulsions, published in Japanese Patent Application Laid-Open No. 57-8283.
No. 1 and No. 60-178445, but it has not yet reached a sufficient level of improvement.Despite many studies, the hydrogen enhancement process in which photosensitive materials are treated with hydrogen gas under vacuum has not yet reached a sufficient level of improvement. The increase in sensitivity was insufficient compared to the sensitivity. This is reported in the Journal of Imagin
g 5science, Vol. 29, p. 233 (1985), by Molsar et al. At the same time, improvements in the storage stability of photographic materials containing reduction-sensitized emulsions have been awaited.

Furthermore, when a reduction sensitizer is used for color sensitization, competition for the generated holes occurs between the highest occupied level of the dye and the reduced silver nucleus in the silver halide, and holes are captured by the dye. 1.11. The probability of recombination between the photoelectrons of the holes increases, and the effect of reduction/enhancement decreases markedly, and this tendency is remarkable in dyes with a high number of highest occupied units. Leubn
er (Lübner) (Photographic 5
Science and Engineering Vol. 22, p. 270 (1978)) and J. E. Jones.
and P, B., Gilman, Jr. (Photogr.
aphic 5science and Engineer
ing l 7 @ page 367 (1973)) et al.

Furthermore, by chemically ripening the grains in the presence of a dye, it is possible to obtain a color-sensitized emulsion with high sensitivity and good storage stability by strengthening the adsorption of the dye and reducing the inherent desensitization caused by color sensitization. This is described in, for example, Japanese Patent Laid-open Nos. 55-26589, 61-103149, and 61-133941.

(Problems to be Solved by the Invention) The conventional technology of reduction sensitization is insufficient to meet the demands of recent high-sensitivity, high-image-quality photographic materials, especially when color sensitization is applied. The trend was remarkable. In addition, conventional reduction sensitization techniques do not sufficiently improve storage stability such as desensitization and sensitization over time, and this tendency is particularly noticeable in cases of Buddhist monks. Furthermore, the method of hydrogen sensitization also has the disadvantage that the sensitizing effect is lost if the photosensitive material is left in the air after hydrogen sensitization. Therefore, it is difficult to utilize this sensitization method in the case of photographic materials for which special equipment cannot be used.

An object of the present invention is to provide an emulsion with high sensitivity and excellent graininess, a color sensitized emulsion with high sensitivity and little fog, and a method for producing a color sensitized emulsion with high sensitivity and excellent storage stability. . A second object is to provide a photographic material with high sensitivity and good graininess, a photographic material with high sensitivity and little fog, and a photographic material with high sensitivity and poor storage stability. The third object is to provide a color photosensitive material with high sensitivity and good graininess, a color photosensitive material with high sensitivity and little fog, and a color photosensitive material with high sensitivity and excellent storage stability.

(Means for Solving the Problems) The above aspects of the present invention were achieved by the following method: (1) In the production process of a silver halide emulsion, reduction sensitization is performed using at least one of ascorbic acid or its derivatives. A method for producing a silver halide emulsion, which comprises: and chemically sensitizing the emulsion in the presence of a spectral sensitizing dye.

(2) 5X10-”-IX per mole of silver halide
2. The method for producing a silver halide emulsion according to claim 1, wherein the reduction sensitization is carried out using to"' moles of ascorbic acid or a derivative thereof.

The present invention will be explained in detail below.

Spectral sensitizing dye> Chemical sensitization (chemical ripening) in the method for producing an emulsion of the present invention
It is essential that the step includes a step carried out in the presence of a spectral sensitizing dye up to the end of deferred delivery. However, the case where the chemical sensitization process is completed by adding a spectral sensitizing dye is also included in the above process. The addition of a dye in the present invention is used for the purpose of making the sensitizing dye act as a control agent for crystal growth during grain formation or a control agent for photonucleation during chemical sensitization. Further, such a dye addition method results in adsorption of the dye onto the particles at a high temperature of 50° C. or higher, and is used for the purpose of promoting enhancement of adsorption.

In the present invention, the end of afterripening refers to the stage at which the progress of chemical sensitization has stopped.

Chemical sensitization in the presence of a spectral sensitizing dye in the present invention can be carried out at any stage of emulsion preparation that has been known to be useful, as long as it is before the completion of chemical ripening. Spectral sensitization can be performed simultaneously with chemical sensitization, as taught in U.S. Pat. Furthermore, spectral sensitization can also be started before the completion of silver halide grain precipitate formation. It is also possible, as taught in U.S. Pat. No. 4,225,666, to have a portion of the spectral sensitizing dye present in the step before chemical sensitization is complete, and the remainder to be introduced after chemical sensitization. be.

That is, the spectral sensitizing dye may be added at any step before grain formation, during grain formation, during physical ripening, or before the water washing step, or before chemical sensitization, during chemical sensitization, or just before the end of chemical sensitization. It may be added at any time.

In addition, the spectral sensitizing dye used in the present invention is disclosed in Japanese Patent Application Laid-Open No. 62-89
It can be used in combination with the nitrogen-containing heterocyclic compound represented by the following general 2 described in No. 952.

General formula (wherein R1 is at least one -COOM or -
SO3M''11I represents a substituted aliphatic group, aromatic group or heterocyclic group, M represents a hydrogen atom, an alkali metal atom, quaternary ammonium or quaternary phosphonium) The amount used is silver halide 1 per mole, 1 x lo-s
~lXl0-" moles, preferably Ixl0-'
~I x 10-' mol.

The spectral sensitizing dye that can be used in the present invention is not particularly limited and can be selected from commonly used methine dyes.

Dyes for use in the present invention include cyanines, merocyanines, complex cyanines and complex merocyanines (i.e., tri-, tetra-1 and polynuclear cyanines and merocyanines);
Included are polymethine dyes including oxol, hemioxonol, styryl, merostyryl and streptocyanin.

Cyanine spectral sensitizing dyes include quinolinium, pyridinium, isoquinolinium, 3H-indolium, benz(
6) Indolium, oxacillium, oxazolinium, thiazolium, thiazolinium, selenazolium, selenacillinium, imidazolium, imidazolinium,
Penzothisazolinium, benzothiazolium, benzoselenazolium, benzimidazolium, naphthoxazolium, naphthothiazolium, naphthoselenazolium, thiazolinium, dihydronaphthothiazolium, sodium and imidazopyrazinium It includes two basic heterocyclic nuclei joined by a methine linkage, as derived from a quaternary salt.

Merocyanine spectral sensitizing dyes include barbituric acid, 2-
Thiobarbic acid, rhodanine, hydantoin, 2-
Thiohydantoin, 4-thiohydantoin, 2-pyrazolin-5-one, 2-inxacillin-5-one, indan-1,3-dione, cyclohexane-1,3-dione, 1,3-dioxane-4,6- cyanine dye types with acidic nuclei such as those derived from diones, pyrazoline-3°5-dione, pentane-2,4-dione, alkylsulfonylacetonitrile, malononitrile, isoquinolin-4-one and chroman-2,4-sion. Examples of blue-sensitive sensitizing dyes containing those in which a basic heterocyclic nucleus is bonded via a methine bond include, for example, US-2493748;
Special Publication No. 46-30023, US-3752670, US
-3976492, JP-A-58-91444, JP-A-6
1289.341. The material described in JP-A-59-55,426 can be used. Examples of green-sensitive sensitizing dyes include:
US-3506443, JP 47-25379, JP 43-4936, JP 62-139,552. JP-A-61-156,046, JP-A-60-128,433
, Japanese Patent Publication No. 49-4650 can be used. In addition, as red-sensitive sensitizing dyes, for example, Japanese Patent Publication No. 43-49
33, Special Publication No. 46-10, 473, Special Publication No. 45-32.
74L JP-A-59-135,461, JP-A-59-21
4,030. JP-A-61-282゜831, JP-A-59
-166.955, JP-A-59-77.443, US-
4,326,023 can be used. Various supersensitization techniques can be used for color sensitization during or in combination with chemical sensitization in the present invention. Examples of useful dye combinations, including superenhancing dye combinations, are provided in U.S. Pat. Nos. 3,506,443 and 3. 672. An example of a supersensitizing combination consisting of a 0-spectral sensitizing dye and a non-light absorbing additive described in U.S. Pat.
1,805, and bis-triazinylaminostilbene as shown in U.S. Pat. No. 2,933,390; 2,937,089, mercapto-substituted heterocyclic compounds as shown in U.S. Patent No. 3,457,078, and British Patent No. 1.413. ,82
Iodide can be used as shown in No. 6.

In addition, as a method for adding a sensitizing dye during the manufacturing process of the emulsion of the present invention, various methods that have been proposed in the past can be applied. Dissolving the dye in a volatile organic solvent,
The solution may be dispersed in a hydrophilic colloid, and this dispersion may be added to an emulsion.Furthermore, the sensitizing dyes of the present invention may be individually dissolved in the same or different solvents and added to an emulsion. These solutions can be mixed or added separately beforehand.

In the present invention, when adding the sensitizing dye to the silver halide emulsion, examples of the dye solvent include methyl alcohol,
Water-miscible organic solvents such as ethyl alcohol and acetone are preferably used.

In the present invention, when the aggravating dye is added to the silver halide emulsion, the amount added is lXl0 per mole of silver halide.
-' mole to 2.5X10-' mole is preferred, more preferably 1.0X10-' mole, Ox 10-' mole.

The enhancing dye can also be used in combination with other enhancing dyes or supersensitizers.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion.

Chemical sensitization In the present invention, it is extremely important to perform chemical sensitization other than reduction sensitization, typified by selenium sensitization, sulfur sensitization, and gold sensitization. The location where chemical sensitization is applied varies depending on the composition, structure, and shape of the emulsion grains, as well as the intended use of the emulsion.

There are cases in which chemical sensitizing nuclei are embedded inside the particles, in cases where they are embedded in shallow positions from the particle surface, or in cases where chemical sensitizing nuclei are created on the surface.6 The effects of the present invention are effective in all cases. Particularly preferred is the case where chemically sensitized nuclei are created near the surface. In other words, surface latent image type emulsions are more effective than internal latent image type emulsions.

In the present invention, chemical sensitization preferably refers to chemical sensitization other than reduction sensitization, and refers to chemical sensitization other than reduction sensitization.
Author, The Photographic Ink Process, 4th edition, Macmillan Publishing, 1977, (T. Il. James,
The Theory of the Photography
phic Process, 4th ed.

MacmHlan, 1977), p. 67, 76, and also Research Disclosure 121.1974.
April, 12008; Research Disclosure,
Volume 34, June 1975, 13452, U.S. Patent No. 2,
No. 642,361, No. 3,297.446, No. 3,7
No. 72,031, No. 3857.711, No. 3,901
, No. 714, No. 4.266.018 and No. 3,90
4,415, as well as pAg 5-10. as described in British Patent No. 1,315,755. At pH 5-8 and temperature 30-80°C, sulfur, selenium, tellurium, gold,
This can be done using platinum, palladium, iridium or a combination of these sensitizers.

As the gold sensitizer used in the present invention, gold complex salts (see, for example, US Pat. No. 2,399,083) can be particularly preferably used.

Among these, potassium chloroaurate, potassium aurithiocyanate, auric trichloride, sodium aurithiosulfate, and 2-oresulfobenzothiazole methochloride are particularly preferred.

The content of the gold sensitizer in the silver halide grain phase is 10-9 to 10-' mol per 1 mol of ill halide, particularly,
10-'' to 10-4 mol is preferred.

In the present invention, it is preferable to use not only gold sensitization but also selenium sensitization or sulfur sensitization.

Examples of sulfur sensitizers used include thiosulfates, thioureas, thiazoles, rhodanines, and other compounds (
Specific example: U.S. Patent No. 1,574.944, U.S. Patent No. 2,4
No. 10,689, No. 2,278.947, No. 2,
728,668, 3.65.6,955, 4,030,928, and 4,067.740), among which thiosulfates and thioureas and rhodanines are particularly preferred.

The amount of sulfur sensitizer depends on the particle size, temperature of chemical sensitization, I)
The optimum amount can be selected depending on the conditions such as Ag, I) [(10-7 to 10-3 per mole of halogenated compound)
mol, preferably 5X10-' to 10-4 mol, more preferably 5X10-' to 10-' mol.

The temperature for chemical sensitization was in the range of 30°C to 90°C, and the pAg was 5.
The pH value can be selected as appropriate between IO and 4 or higher.

In the present invention, a sensitization method using metals such as iridium, platinum, rhodium, palladium, etc. (for example, U.S. Pat.
No. 48.060, 2. 566, No. 245, same 2,
566.263) and a selenium sensitization method using a selenium compound can also be used in combination.

Chemical sensitization can also be carried out in the presence of chemical sensitization aids. The chemical sensitization aid used is a compound known to suppress fog and increase sensitivity during the chemical sensitization process, such as azaindene, azapyridazine, and azapyrimidine. Examples of chemical sensitization aid modifiers include U.S. Pat. No. 2,131.038, U.S. Pat. "Photographic Emulsion Chemistry", 138-143
It is written on the page.

Ascorbic Acid> The ascorbic acid compound used in the present invention is desirably used in a larger amount than the amount added in conventional reduction sensitizers. For example, Japanese Patent Publication No. 57-33572 states that ``The amount of reducing agent is usually 0.75
An amount of 0.1 to 10 cm per kg of silver nitrate (as ascorbic acid, 10 to 10 S mol/A g
X moles) is often effective. ” (converted value is by the inventors). US-2,487,8
50 states, "The amount of tin compound that can be used as a reduction sensitizer is 1X10-' to 44X10-" moles.
It states: Also, in JP-A-57-179835,
The amount of thiourea oxide added is about 0.01 to about 2 Akebono per mole of silver halide, and the amount of stannous chloride is about 0.01 to about 2 Akebono.
The preferred amount of the ascorbic acid compound used in the present invention depends on factors such as emulsion grain size, halogen composition, emulsion preparation temperature, p) (, pAg, etc.). It is preferable to select from the range of 5×10-'mol-1X10-' mol per 1 mol of silver halide, and more preferably from the range of 5×10-4 mol to IX10-'' mol, although it depends on the amount. Particularly preferred is txio-3 mol-lXl0-'
It is a matter of choosing from a range of moles.

Examples of the ascorbic acid compound used in the present invention are shown below, but the ascorbic acid used in the present invention is not limited thereto.

(A-1) L-ascorbic acid (A-2) Sodium L-ascorbate (A-
3) Potassium L-ascorbate (A-4) D
L-ascorbic acid (A-5) Sodium D-ascorbate (A-6
) L-ascorbic acid-6-acetate (A-7) L-ascorbic acid-6-palmitate (A-8) L-ascorbic acid #1-6-benzoate (A-9) L-ascorbic acid-6-diacetate (A-10) L-Ascorbic acid-5.6-0-isopropyl To add the above-mentioned ascorbic acid compounds in the production process of the silver halide emulsion of the present invention, they may be directly dispersed in the emulsion. Alternatively, it may be added during the manufacturing process after being dissolved in a solvent such as water, methanol, or ethanol alone or in a mixed solvent.

The ascorbic acid compound of the present invention may be added at any stage of the emulsion manufacturing process. Alternatively, a reduction sensitizer may be added in advance to an aqueous solution of a water-soluble root salt or a water-soluble alkali halide, and these aqueous solutions may be used to form particles. It is also a preferable method to add the solution of the reduction sensitizer in several portions or continuously over a long period of time as the particles are formed.

The reduction sensitization method using the ascorbic acid compound of the present invention is superior to conventional reduction sensitization methods in terms of sensitivity, fog, and stability over time. It is more preferable in some cases.

Thiosulfonic acid compound> The thiosulfonic acid compound used in the present invention is a compound of general formula (1) or DI),
It may also be a polymer containing a divalent group derived from the structure shown in II) as a repeating unit. Furthermore, when possible, R, R', R1, and L may be bonded to each other to form a ring.

To explain in more detail the compounds of general 2N), [1) and ([[), when R, R' and RZ are aliphatic groups, saturated or unsaturated, linear, branched or cyclic aliphatic groups, The group hydrocarbon group is preferably an alkyl group having 1 to 22 carbon atoms, an alkenyl group or an alkynyl group having 2 to 22 carbon atoms, and these 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 group and butynyl group.

The aromatic groups for R, R' and R3 include monocyclic or condensed ring aromatic groups, preferably those having 6 to 20 carbon atoms, such as phenyl and naphthyl. These may be substituted.

The heterocyclic group of R, R' and R2 includes nitrogen, oxygen,
3 to 1 having at least one element selected from sulfur, selenium, and tellurium and having at least one carbon atom
A 5-membered ring, preferably a 3- to 6-membered ring, such as pyrrolidine, hyperidine, pyridine, tetrahydrofuran, thiophene, oxazole, thiazole,
Examples include imidazole, benzothiazole, benzoxazole, henzimidazole, selenazole, benzoselenazole, tetrazole, triazole, benzotriazole, tetrazole, oxadiazole, and thiadeazole ring.

Substituents for R, R' and R2 include, for example, alkyl groups (e.g. methyl, ethyl, hexyl), alkoxy groups (e.g. methoxy, ethkyne, octyl), aryl groups (e.g. phenyl, naphthyl, tolyl), hydroxy groups. , halogen atoms (fluorine, chlorine, bromine, iodine), aryloxy groups (e.g. phenoxy), alkylthio groups (
For example, methylthio, butylthio), arylthio group (
For example, phenylthio), acyl groups (for example, acetyl, propionyl, butyryl, valeryl), sulfonyl groups (for example, eva, methylsulfonyl, phenylsulfonyl),
Acylamino group (e.g. acetylamino, benzoylamino), sulfonylamino group (e.g. methanesulfonylamino, benzenesulfonylamino), acyloxy group (e.g. acetoxy, benzoxy), carboxyl group, cyano group, sulfo group, amino group, - SO! S M
group (M represents a monovalent cation), and -3O□R' group.

The divalent linking group represented by is an atom or atomic group containing at least one selected from C, N, S, and O. Specifically, an alkylene group, an alkenylene group, an alkynylene group, Arylene group, OS N HCO
It consists of SOz- or the like alone or in combination.

L is preferably a divalent aliphatic group or a divalent aromatic group. The divalent aliphatic group of L is, for example, +Chz→-
, (n=1-12), CHz-CH=CHCHz- -CH! C= CCHz − can be obtained. Examples of the divalent aromatic group for L include phenylene and naphthylene.

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

M is preferably a metal ion or an organic cation. Examples of metal ions include lithium ions, sodium ions, and potassium ions. Organic cations include ammonium ions (e.g. ammonium, tetramethylammonium, tetrabutylammonium)
, phosphonium ion (tetraphenylphosphonium)
, guanisine group, etc.

Specific examples of the compounds represented by the general formula (1), [■] or (III) are listed in Table A, but the invention is not limited thereto.

The compound of general formula (1) can be easily synthesized by the method described in JP-A-54-1019 and British Patent No. 972.211.

The compound represented by the general formula [1], (n) or (III) has an amount of 10-7 to 10-1 per 111 moles of halogen.
It is preferable to add moles of 10-' to 10-
! In particular, an amount of 104 to 10-'' moles of Ag is preferred.

The compounds represented by formulas (1) to (In) can be added during the manufacturing process by a method commonly used for adding additives to photographic emulsions.

For example, for water-soluble compounds, make an aqueous solution of an appropriate concentration,
Compounds that are insoluble or sparingly soluble in water are dissolved in a suitable organic solvent that is miscible with water, such as alcohols, glycols, ketones, esters, amides, etc., and does not adversely affect photographic properties. However, it can be added as a solution.

The compound represented by compound (1), (II) or (Ill) may be added at any stage during grain formation of the silver halide emulsion, before or after chemical sensitization, preferably during reduction. In this method, a compound is added before or during sensitization.

It may also be added to the reaction vessel in advance. Alternatively, compounds (1) to (III) may be added in advance to an aqueous solution of a water-soluble root salt or a water-soluble alkali halide, and these aqueous solutions may be used to form particles. It is also a preferable method to add the solutions of ) to (III) in several portions or continuously over a long period of time.

The general formula of the most preferred compound for the present invention is the general formula [! ] It is a compound that is produced by

The silver halide color photographic light-sensitive material of the present invention, including emulsions, couplers, and additives that can be used in the present invention, has at least one emulsion layer containing a silver halide emulsion obtained by the production method of the present invention on a support. have

The photosensitive material of the present invention may contain a negative photosensitive silver halide produced by a method other than the production method of the present invention. The photosensitive material of the present invention preferably contains at least one yellow coupler. a blue-sensitive silver halide emulsion layer containing at least one magenta coupler, a green-sensitive silver halide emulsion layer containing at least one cyan coupler, and a red-sensitive silver halide emulsion layer containing at least one cyan coupler on a support. have Furthermore, the present invention is suitable as a color negative film or color reversal film for high-sensitivity photography, and ■ So sensitivity is 400 or higher, preferably 800 or higher and 640
Sensitivity down to 0 can be achieved.

In the color photographic light-sensitive material of the present invention, in order to have high sensitivity, improve graininess, or improve color reproduction due to the glabella multilayer effect, it is necessary to provide a multilayer film with a plurality of emulsion layers having the same color sensitivity but different light sensitivities. Preferably, it is a color photographic material.

It is preferable to use the emulsion obtained by the production method of the present invention in the highest sensitivity layer of the light-sensitive material of the present invention.

In a multilayer silver halide color photographic light-sensitive material, the unit photosensitive layers are generally arranged in the following order from the support side: a red-sensitive layer, a green-distracting layer, and a blue-sensitive layer. However, depending on the purpose, the order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layer.

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

The intermediate layer includes JP-A Nos. 61-43748 and 59-1.
No. 13438, No. 59-113440, No. 61-20
Coupler, DIR compound, etc. as described in No. 037 and No. 61-20038 may be included,
It may also contain a commonly used color mixing inhibitor.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are composed of a high-speed emulsion layer and a low-speed emulsion layer, as described in West German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer structure can be preferably used. Usually, it is preferable to arrange the halogen emulsion layers so that the photosensitivity decreases toward the support, and a non-photosensitive layer is provided between each halogen emulsion layer. It may be. In addition, JP-A-57
-112751, 62-200350, 62-
As described in Nos. 206541 and 62-206543, a low-sensitivity emulsion layer may be provided on the side far from the support, and a high-sensitivity emulsion layer may be provided on the side close to the support.

As a specific example, from the side farthest from the support, low sensitivity blue sensitive layer (BL) / high sensitivity blue sensitive layer (BH) / high sensitivity green sensitive layer (GH) / low sensitivity green sensitive layer (GL) /high sensitivity red light sensitive layer (RH)/low sensitivity red light sensitive layer (RL) order, or B H/B L/G L/GH/RH/RL order,
Alternatively, they can be installed in the order of B H/B L/GH/GL/RL/RH.

Or, as described in Japanese Patent Publication No. 55-34932, the blue-sensitive layer/G H
They can also be arranged in the order of /RH/GL/RL. Alternatively, as described in JP-A-56-25738 and JP-A-62-63936, blue-sensitive 1/GL/RL/GH/RH can also be arranged in the order of blue sensitivity from the side farthest from the support. .

In addition, as described in Japanese Patent Publication No. 49-15495, the upper layer is a silver halide emulsion layer with the highest sensitivity, the middle layer is a silver halide emulsion layer with lower sensitivity, and the lower layer is more sensitive than the middle layer. An example is an arrangement consisting of three layers having different photosensitivity, in which a silver halide emulsion layer with a low density is arranged and the photosensitivity is sequentially imaged toward the support.

Even in the case where the layer is composed of three layers with different photosensitivity, as described in JP-A No. 59-202464, medium-sensitivity emulsion is added from the side remote from the support in the same color-sensitive layer. They may be arranged in the following order: layer/high-speed emulsion layer/low-speed emulsion layer.

In the photographic emulsion layer of the photographic light-sensitive material used in the present invention, any silver halide including silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride may be used. Preferred silver halides are silver iodobromide, silver bromide, and silver chlorobromide containing up to 30 mol % of silver iodide.

Even if the silver halide grains used in the present invention are normal crystals that do not contain twin planes, examples such as those explained in Basic Silver Salt Photography of the Photographic Industry (Corona Publishing), edited by the Photographic Society of Japan, p. 163,
For example, a single twin with one twin plane, two parallel twin planes
Depending on the purpose, it can be selected from among parallel multiple twins containing two or more nonparallel twin planes, nonparallel multiple twins containing two or more nonparallel twin planes, and the like. In the case of normal crystals, it is a cube consisting of (100) planes, an octahedron consisting of (111) planes, and Japanese Patent Publication No. 55427.
37, disclosed in Japanese Patent Application Laid-Open No. 60-222842 (1
10) Dodecahedral particles consisting of faces can be used.

In addition, Journal of ImagingScie
nce Vol. 30, p. 247 As reported in 1986, (hl) surface positioner with (211) as a representative, (
(331) is the representative surface, (h k O) surface is representative of the (210) surface, and (321) surface is the representative (hkl) surface, although the preparation method requires some ingenuity, but it is possible to It can be selected and used accordingly. (100) plane and (
111) A tetradecahedral particle whose faces coexist in one particle, (1
Particles in which 00) and (110) planes coexist or (11
1) Particles in which two or many planes coexist, such as particles in which a plane and a (110) plane coexist, can also be selected and used depending on the purpose.

The grain size of silver halide may be fine grains of 0.1 micron or less or large grains with a projected area diameter of up to 10 microns, and may be a monodisperse emulsion with a narrow distribution or a polydisperse emulsion with a wide distribution. good.

A so-called monodisperse silver halide emulsion having a narrow grain size distribution in which 80% or more of all grains fall within ±30% of the average grain size in terms of grain number or weight can be used in the present invention. In addition, in order to satisfy the target gradation of a light-sensitive material, two or more types of monodisperse silver halide emulsions with different grain sizes are mixed in the same layer or in separate layers in emulsion layers having substantially the same color sensitivity. Can be applied in multiple layers. Furthermore, two or more types of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion may be mixed or layered for use.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Grafkide, published by Paul Montell (P.

Glafkides, Chimie et Phy
sique Photographique Paul
Montel+ 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G, F, Duff
in.

Photographic Emulsion C
hemistry (Focal Press.

1966), “Manufacture and Coating of Photographic Emulsions” by Zelikman et al.
, Published by Focal Press (Sill, Zelikmanet
al+ Making and Coating P
photographic [! mulsion+Poca
1 Press, 1964). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble root salt with the soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. good.

It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method). As a form of simultaneous mixing method, pAg in the liquid phase in which silver halide is produced is
The method of keeping constant is the so-called chondral
A double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

The above-mentioned silver halide emulsion consisting of regular grains can be obtained by controlling pAg and pH during grain formation. For more information, please see Photographic Science
and Engineering (Photographic
5science and engineering)
Vol. 6, pp. 159-165 (1962); Journal
Of Photographic Science (Journal
of Photographic 5science),
12, pp. 242-251 (1964), U.S. Patent No. 3
．． 655,394 and British Patent No. 1,413,74
It is stated in No. 8.

Further, tabular grains having an aspect ratio of 3 or more can also be used in the present invention. Tabular grains are described in ``Theory and Practice of Photography'' by C1eve, Photograp
hyTheoryandPractice (193
0)), p. 131; Gutoff, Photographic Science and Engineering (Gutoff,
Photographic Science and I
! ngineering), Volume 14, 248″+25
7 pages (1970); U.S. Patent Nos. 4,434°226, 4,414.310, 4,433.048,
4,439,520 and British Patent No. 2,112,
It can be easily prepared by the method described in No. 157 and the like. The use of tabular grains has advantages such as increased covering power and increased color sensitization efficiency by sensitizing dyes, which are detailed in U.S. Pat. No. 4,434,226 cited above. .

Tabular grains are preferred as emulsions of the present invention.

In particular, particles with an aspect ratio of 3 to 8 account for 50% of the total projected area.
Tabular grains occupying the above amount are preferable.

The crystal structure may be --like, the inside and outside may have different halogen compositions, or it may have a layered structure. These emulsion grains are described in British Patent No. 1.027.
No. 146, U.S. Patent No. 3.505.068, U.S. Patent No. 4,4
44,877 and Japanese Patent Application No. 58-248469. Furthermore, silver halides having different compositions may be bonded by epitaxial bonding, or compounds other than silver halide such as silver rhodan or lead oxide may be bonded.

The silver halide emulsion of the present invention preferably has a distribution or structure regarding the halogen composition in its grains.
Typical examples are JP-B No. 43-13162 and JP-A No. 6.
These are core-shell type or double-structured particles in which the interior and surface layers of the particles have different halogen compositions, as disclosed in JP-A No. 1-215540, JP-A-60-222845, JP-A-61-75337, and the like. In such particles, the shape of the core portion and the overall shape including the shell may be the same or different. Specifically, the core part has a cubic shape, and the shape of the shelled particle is sometimes cubic or octahedral.Conversely, the core part is octahedral and the shelled particle is cubic or octahedral. Sometimes it has the shape of a facepiece. Further, although the core portion is a clearly regular particle, the shape of the shelled particle may be slightly distorted or irregular. In addition, instead of a simple double structure, it is possible to create a triple structure as disclosed in JP-A No. 60-222844, or a multilayer structure with more than that, or a halogen with a different composition on the surface of the core-shell double structure particle. You can apply a thin layer of silver.

In order to give a structure to the inside of a particle, it is possible to create a particle having not only the above-mentioned enveloping structure but also a so-called bonding structure. These examples are disclosed in Japanese Patent Application Laid-Open No. 59-13354.
0, Japanese Patent Publication No. 58-108526, EP199290A2
, Japanese Patent Publication No. 58-24772, Japanese Patent Application Laid-Open No. 59-16254, etc. The crystal to be bonded can have a composition different from that of the host crystal and can be formed by bonding to an edge, part of a corner, or surface of the host crystal.

Such a bonded crystal can be formed even if the host crystal is uniform in terms of halogen composition or has a core-shell structure.

In the case of a bonded structure, a combination of silver halides is naturally possible, but a bonded structure can be obtained by combining a silver halide with a silver salt compound that does not have a rock salt structure, such as silver rhodan or silver carbonate. Further, a non-silver salt compound such as Pbo may also be used if a bonded structure is possible.

In the case of silver iodobromide grains having these structures, for example, in a core-shell type grain, even if the core part has a high silver iodide content and the shell part has a low silver iodide content, or conversely, the core part has a low silver iodide content. Grains with a low silver iodide content and a high shell part may be used. Similarly, grains with a bonded structure may have a high silver iodide content in the host crystal and a relatively high silver iodide content in the bonded crystal. It may be a low particle or vice versa.

In addition, the boundaries between particles with these structures with different halogen compositions may be clear boundaries, or may be unclear boundaries due to the formation of mixed crystals due to composition differences, or may be actively continuous boundaries. It may also be one with some structural changes.

The silver halide emulsion used in the present invention is EP-009672.
781, EP-0064412B1, etc., or DE-2
The surface may be modified as disclosed in JP-A-60-221320, No. 306447C2.

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

It is known that silver halide solvents are useful in promoting ripening. For example, it is known to have an excess of halide ions present in the reactor to promote ripening. It is therefore clear that ripening can be accelerated simply by introducing a halide salt solution into the reactor. Other ripening agents can be used, and these ripening agents can be incorporated in their entirety into the dispersion medium in the reactor before the silver and halide salts are added, and one or more ripening agents can be used. can also be introduced into the reactor along with the addition of halide salts, silver salts or peptizers. As a further variant, the ripening agent can also be introduced independently at the halide salt and silver salt addition stages.

As ripening agents other than halogen ions, ammonia or amine compounds, thiocyanate salts such as alkali metal thiocyanate salts, especially sodium and potassium thiocyanate salts, and ammonium thiocyanate salts can be used.

The photographic emulsion used in the present invention can contain 19 various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroimidazoles, nitrobeni/zimidazoles, chlorobenzimidazoles,
Bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles! ! [(especially 1
-phenyl-5-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines; thioketo compounds, such as oxadorinthione; azeindenes; 3, 3a, 7
A number of compounds known as antifoggants or stabilizers can be added, such as tetraazaindenes), pentaazaindenes, etc. For example, US Patent 3
, No. 954,474, No. 3,982.947, and Japanese Patent Publication No. 52-28,660 can be used.

The various additives described above are used in the photosensitive material related to the present technology, but various other additives can also be used depending on the purpose.

These additives are described in more detail in Research Disclosure 1 tem 17643 (December 1978) and Summer Tea 18716 (November 1979), and the relevant parts are summarized in the table below.

Additive type 11 RD17643 RD187
161 Chemical sensitizers Page 23 Page 648 Right column 2 Sensitivity increasing agents Same as above 4 Brightening agents Page 24 8 Dye image stabilizers Page 25 9 Hardening agents Page 26 651 True left column lO binder 26 True Same as above 11 Plasticizers, lubricants Page 27 Page 650 Right column Various color couplers can be used in the present invention,
A specific example is the research disclosure mentioned above (
RD) Nal 7643, ■-C-G.

As a yellow coupler, for example, U.S. Patent No. 3.93
3.501, same No. 4,022,620, same No. 4,3
No. 26.024, No. 4.401゜752, Special Publication No. 5
No. 8-10739, British Patent No. 1.425,020,
Same 1st. 476, 760, etc. are preferred.

As magenta couplers, 5-pyrazolone and pyrazoloazole compounds are preferred, for example, US Pat.
．． 310,619, European Patent No. 4,351.897, European Patent No. 73.636, US Patent No. 3.061.432
No. 3,725゜067, Research Disclosure 24220 (June 1984), JP-A No. 6
No. 0-33552, Research Disclosure Magnet 2
4230 (June 1984), JP-A-60-43659
No. 4,500,630, U.S. Pat. No. 4,540
．． Particularly preferred are those described in No. 654, etc.

Cyan couplers include phenolic and naphthol couplers, and are described in U.S. Pat. No. 4,052,212.
No. 4.146,396, No. 4.228,23
No. 3, No. 4. 296. No. 200, No. 2,369
．． No. 929, No. 2,801.171, No. 2,7
No. 72,162, No. 2.895,826, No. 3,
No. 772,002, No. 3,758.308, No. 4
．． No. 334.011, No. 4.327,173, West German Patent Publication No. 3.329.729, European Patent No. 121.
No. 365A, U.S. Patent No. 3. 446. No. 622, No. 4,333,999, No. 4,451.559,
4.427,767, European Patent No. 161,626
Those described in item A are preferred.

Colored couplers for correcting unnecessary absorption of coloring dyes are described, for example, in Research Disclosure No. 1764.
Section 3 ■-G, U.S. Patent Cylinder 4. No. 163.670, Japanese Patent Publication No. 57-39413, U.S. Patent No. 4,004,92
No. 9, No. 4,138゜258, British patent tube 1.14
6,368 is preferred.

Examples of couplers whose coloring dyes have appropriate diffusivity include U.S. Patent No. 4,366.237, British Patent No. 2,
125,570, European Patent No. 96.570 and West German Patent Publication No. 3,234°533 are preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat. No. 3,451,820, U.S. Pat.
It is described in No. 73, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers releasing development inhibitors include the aforementioned RD17643,
Patents listed in Sections ■-F, Japanese Patent Application Laid-Open No. 57-151944
Preferred are those described in No. 57-154234, No. 60-184248, and U.S. Pat.

As a coupler that releases a nucleating agent or a development accelerator imagewise during development, for example, British Patent No. 2°097.14
No. 0, No. 2,131,188, JP-A-59-157
Those described in No. 638 and No. 59-170840 are preferred.

Other couplers that can be used in the photosensitive material of the present invention include, for example, the competitive couplers described in U.S. Pat. No. 4,130.427, and U.S. Pat.
No. 4,338,393, No. 4,310,61
Multi-light coupler described in No. 8 etc., JP-A-60-1859
DIR redox compounds or DIR coupler-releasing couplers or DIR coupler-releasing couplers or redoxes described in European Patent No. f73,302A, such as those described in European Patent No. f73,302A; For example, R,D.

Magnet 11449, 24241, JP-A-61-20124
Bleach accelerator releasing couplers such as those described in U.S. Patent No. 4. ．． 553,477, and the like.

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

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

Specific examples of high boiling point a-containing solvents with a boiling point of 175°C or higher at normal pressure used in the oil-in-water dispersion method include phthalic acid esters (e.g., dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalates), esters of phosphoric or phosphonic acids (e.g. tripel phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate), benzoic acid esters (e.g. -ethylhexylbenzoate, F-decylbenzoate, 2-ethylhexyl-p-hydroxybenzoate), amides (e.g., N,N-diethyldodecanamide, N,N-diethyllaurylamide, N-tetradecylpyrrolidone),
Alcohols or phenols (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, trioctyl citrate), aniline derivatives (e.g. N, N-dibutyl-2-butoxy-5-t)
ert-octylaniline), hydrocarbon'M (e.g.
paraffin, dodecylbenzene, diisopropylnaphthalene), etc. Further, as the auxiliary solvent, an organic solvent having a boiling point of about 30°C or higher, preferably 50°C or higher and about 160°C or lower can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2- Examples include ethoxyethyl acetate and dimethylformamide.

Specific examples of latex dispersion processes, effects, and latex for impregnation include U.S. Pat. It is described in.

The present invention can be applied to various color photosensitive materials. Typical examples include color negative film for general use or movies, color reversal film for slides or television, color paper, color positive film, and color reversal paper.

When the present invention is used in color photographic materials, it can be applied to photosensitive materials with various configurations and photosensitive materials in which layer configurations and special color materials are combined.

A typical example is illustrated below. JP 47-49031, JP 49-3843, JP 50-21248, JP 59-38147, JP 59-60437,
JP 60-227256, JP 61-4043, JP 61-43743, JP 61-42657
A combination of the coupling speed and diffusivity of a color coupler and the layer structure, as shown in No. Special Public Service 1977-15
No. 495, U.S. Pat. No. 3,843,469, in which the same color-sensitive layer is divided into two or more layers, Japanese Patent Publication No. 1983-370
No. 17, Japanese Patent Publication No. 53-37018, Japanese Patent Publication No. 51-49
No. 027, JP-A-52-143016, JP-A-53-
No. 97424, JP-A-53-97831, JP-A-62
Examples include those in which the arrangement of high-sensitivity layers and low-sensitivity layers and the arrangement of layers with different color sensitivities are stipulated, such as No. 200350 and JP-A-59-177551.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, page 28 of 17643, and 6 of the same patient 1B716
It is described from the right column of page 47 to the left column of 648.

The color photographic material according to the present invention includes the above-mentioned RD, N
117643, 28-29, and consent 18716, 651, left column to right column.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but p-phenylenediamine compounds are preferably used, representative examples of which include 3-methyl-4-amino-N, N-diethylaniline, 3- Methyl-4-amino-N-ethyl-N
β-hydroxyethylaniline, 3-methyl4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β
-methoxyethylaniline and their sulfates, hydrochlorides, p-)luenesulfonates, and the like.

Two or more of these compounds can be used in combination depending on the purpose.

The color developer may contain pH buffering agents such as alkali metal carbonates, borates or phosphates, bromide salts, iodide salts,
Development inhibitors or anticapri agents such as benzimidazoles, benzothiazoles or mercapto compounds are generally included. If necessary, hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenyl semicarbazides, triethanolamine, catechol sulfonic acids, triethylenediamine (1,4-diazabicyclo[2°2.2]octane), etc. Various preservatives, 7R organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts,
Development accelerators such as amines, dye-forming couplers, fogging agents such as competing couplers sodium boron hydride, auxiliary developing agents such as 1-phenyl-3-birazolyne, tackifiers, amino acids, polycarboxylic acids. , aminopolyphosphonic acid, alkylphosphonic acid, phosphonocarboxylic acid, etc., such as ethylenediaminetetraacetic acid, nitrilo-P#j11 diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyl Ethyliminodiacetic acid, 1-hydroxyethylidene-1,1 diphosphonic acid, nitrilo-N,N,N-)rimethylenephosphonic acid, ethylenediamine-N,N.

Representative examples include N',N'-tetramethylenephosphonic acid, ethylene diamine-di(0-hydroxyphenylacetic acid), and salts thereof.

Further, when performing reversal processing, black and white development is usually performed and then color development is performed. This black and white developer contains known black and white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-virapriton, or aminophenols such as N-methyl-p-aminephenol. It can be used alone or in combination.

The pH of these color developing solutions and black and white developing solutions is generally 9 to 12. The amount of replenishment of these developing solutions depends on the color photographic light-sensitive material to be processed, but it is generally less than 31 per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher,
It can also be set to 1 or less. When reducing the amount of replenishment, it is preferable to prevent evaporation of the solution and air oxidation by reducing the contact area with the air in the processing tank, and by using means to suppress the accumulation of bromide ions in the developer. It is also possible to reduce the amount of replenishment.

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

After color development, the photographic emulsion layer is usually bleached.

The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or separately, or in order to speed up the process, a bleach-fixing process may be performed after the bleaching process. Furthermore, treatment with two consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment can be carried out as desired depending on the purpose. As a bleaching agent, for example, iron ([[I), Kobal]
(11) Compounds of polyvalent metals such as chromium (■) and copper (II), peracids, quinones, nitro compounds, etc. are used.

Typical bleaching agents include ferricyanide; dichromate; organic complex salts of iron (l[[) or cobalt (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, l,3 -Aminopolycarboxylic acids such as diaminopropanetetraacetic acid and glycol ether diaminetetraacetic acid, or complex salts of citric acid, tartaric acid, malic acid, etc.;
Persulfates; bromates; permanganates; nitrobenzenes and the like can be used. Among these, aminopolycarboxylic acid iron (III) complex salts and persulfates, including ethylenediaminetetraacetic acid iron (III) complex salts, are preferable from the viewpoint of rapid processing and environmental pollution prevention. T! Salts are particularly useful in both bleach and bleach-fix solutions.

The pH of the bleaching solution or bleach-fixing solution using these aminopolycarboxylic acid iron (Ill) complex salts is usually 5.5 to 8, but in order to speed up the processing, the pH may be lowered. can.

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary.

Specific examples of useful bleach accelerators are found in U.S. Pat. No. 3,893.
It is described in the specification in No. 858 and the like. Furthermore, the compounds described in US Pat. No. 4,552,834 are also preferred; these bleach accelerators may be added to the sensitive material. These bleach accelerators are sometimes effective when bleach-fixing color light-sensitive materials for photography.

Examples of fixing agents include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used, and ammonium 100sulfate is the most common. Can be used widely. As the preservative for the bleach-fix solution, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to water washing and/or stabilization steps after desilvering treatment.

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used, such as couplers), the application, the temperature of the washing water, the number of stages in the washing tank, the replenishment method (countercurrent, forward flow, etc.), and various other conditions. Can be set over a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is
Urnalof the 5ociety of Mo
tion Picture and Televisi
onEngineers Vol. 64, P, 248-253
(May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. The problem arises. In the processing of the color photosensitive material of the present invention, as a solution to such problems,
The method for reducing calcium ions and magnesium ions described in JP-A-61-131.632 can be used very effectively. Also, JP-A-57-8,542
Chlorinated disinfectants such as isothiazolone compounds, cyabendazole, chlorinated sodium isocyanurate, and other benzotriazoles described in the issue, "Chemistry of antibacterial and fungicidal agents" by Hiroshi Horiguchi, Hygiene Technology Society & I [Microbial It is also possible to use disinfectants described in "Sterilization, Disinfection, and Anti-Mildew Techniques" and "Encyclopedia of Antibacterial and Antifungal Agents" edited by the Japan Antibacterial and Antifungal Society.

The pH of the washing water in the processing of the photosensitive material of the present invention is 4-
9, preferably 5-8. The washing water temperature and washing time can also be set variously depending on the characteristics of the photosensitive material, its use, etc., but generally it is 20 seconds to 10 minutes at 15-45°C, preferably 20 minutes.
A range of 30 seconds = 5 minutes at 5-40°C is selected. Furthermore,
The light-sensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water. In such stabilization treatment, Japanese Patent Application Laid-Open Nos. 57-8.543 and 58-14.8
All known methods described in No. 34 and No. 60-220,345 can be used.

Further, following the water washing treatment, a further stabilization treatment may be carried out, and an example thereof is a stabilization bath containing formalin and a surfactant, which is used as a final bath for color photosensitive materials for shadows. can.

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

The overflow liquid from water washing and/or replenishment of the stabilizing liquid can be reused in other processes such as the desilvering process.

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 processing.

The silver halide color light-sensitive material of the present invention may optionally contain various 1-phenyl-3
- Pyrazolidones may be incorporated. Typical compounds are disclosed in JP-A-56-64,339 and JP-A-57-144,547.
No. 58-115.438, etc.

The various processing solutions used in the present invention are used at a temperature of 10°C to 50°C. Normally, the temperature is 33°C to 38°C, but higher temperatures may be used to accelerate the processing and shorten the processing time, or vice versa. It is possible to improve the image quality and the stability of the processing solution by lowering the temperature. In addition, in order to save silver on photosensitive materials, West German Patent No. 2.226.770 or U.S. Patent No. 3
．． A treatment using cobalt intensification or hydrogen peroxide intensification as described in No. 674.499 may also be carried out.

Further, the silver halide photosensitive material of the present invention is disclosed in U.S. Patent No. 4,
No. 500,626, JP-A-60-133449, No. 5
It can also be applied to the heat-developable photosensitive materials described in European Patent No. 9-218443, European Patent No. 61-238056, European Patent No. 210,660A2, and the like.

Further explanation will be given below by showing examples.

Example 1 2 with an average iodine content of 26 mol% ordinal equivalent diameter of about 1 μm
The core-shell ratio is 1:2 using the Chondrold double-jet method in an aqueous gelatin solution using heavy twinned particles as seed crystals.
, the iodine content of the shell is 5 mol%, the average iodine content is 12
An emulsion consisting of twinned grains with an average equivalent sphere diameter of 1.2 μm was formed so as to have a molar percentage of 1.2 μm.

After grain formation, the emulsion was subjected to a conventional desalting water washing step to obtain a pAg of 8.9. It was redispersed under the conditions of pH 6.3. This unchemically sensitized emulsion was designated as Em-1.

On the other hand, an emulsion prepared in the same manner by adding L-ascorbic acid 1 minute after the start of shell formation was designated as Ern-■.

Table-1-1 Pigment addition method A. Added at the start of chemical sensitization after washing with desalinated water.

B Added when 80% of the entire ripening process is completed during chemical sensitization ripening.

C After chemical sensitization, the temperature was lowered to 40°C and added.

Table 1-2 To the unchemically sensitized emulsion prepared in this manner, the following spectral sensitizing dyes were added at a concentration of 3% per mole of silver at the times indicated below.
Add 10-'mol of -1,! −
2, I-3, ll-1, ll-2, and n-3 were produced.

Chemical sensitization was performed at 60°C.

Spectral sensitizing dye (CHz) zs(h” (CHz) 5sO
Ja When 70% of the entire process during gold/sulfur sensitization of the above emulsion 1-1.2.3 was completed, L ~ ascorbic acid was added,
Emulsions m-1, 2, 3, 4, and 5 were prepared. In addition, emulsion [
The following thiosulfonic acid compound was added at the time of adjustment waiting for 1-3, 4, and 5 and the start of sulfur sensitization, and emulsion rv-i, 2.3
was created.

CzHsS OlS Na Table 1-3 Table 1-4 When preparing unchemically sensitized emulsion Em-1, 80% of grain formation
% of the aforementioned spectral sensitizing dye per mole of silver.
After adding mol of X l O-' to form grains and undergoing the same desalting and washing process as Em-LII, optimally chemically sensitized emulsions V-1 and v-n were prepared.

The emulsion of the present invention and the comparative emulsion thus prepared were coated on a triacetylcellulose film support provided with an undercoat layer in the coating amounts shown in Table 1-4.

Table 1-5 +1+ Emulsion layer Emulsion (1.7X10-"mol/d) Coupler (1,5XlO""mol/rtr>tricresyl phosphate (1,10g/rd) Gelatin ( 2,30g/rd) (2) Protective layer 2.4-dichlorotriazine-6-hydroxy-3-triazine sodium salt (0,08g/r+f) Gelatin (1,8og/rd) for sensitometry on these samples Exposure was applied and the following color development process was performed.

The concentration of the treated sample was measured using a green filter.

The results of the photographic performance obtained are shown in Table 1-6.

The development process used here was carried out at 38°C under the following conditions.

! , Okara image... 2 minutes 45 seconds 2, drifting
White...6 minutes 30 seconds 3 degrees water wash...
...3 minutes 15 seconds 4, established...
・6 minutes 30 seconds 5, washing with water...3 minutes 15
6 seconds, stable...3 minutes 15 seconds The composition of the treatment liquid used in each step is as follows.

Color developer Sodium nitrilotriacetate 1.4g Sodium sulfite 4.0g Sodium carbonate
30.0g potassium bromide
1.4g hydroxylamine sulfate 2
．． 4g4-(N-Ethyl-N-βhydroxyethylamino)-2-methyl-aniline sulfate 4.5g Add water 11 Bleach solution Ammonium bromide 160.0g Aqueous ammonia (28%) 25.0d Ethylenediamine-4 Sodium acetate salt 130g glacial acetic acid
Add 14m water
11 Fixer Sodium tetrapolyphosphate 2.0g Sodium sulfite 4.0g Ammonium thiosulfate (70%) 175.0d Sodium bisulfite 4.6g Add water
lIl Stabilizer Formalin 8.0 - Add water 11 Dew point is 10 seconds and 1
A normal wedge exposure was performed at /100 seconds.

The light source used was one whose color temperature was adjusted to 4800° using a filter, and a yellow filter (5C-52 manufactured by Fuji Photo Film) was used to extract yellow light. Sensitivity was compared based on fog and optical density of 0.2. Sensitivity was expressed as relative sensitivity, with the sensitivity of the sample using emulsion Em-1 being 100. (1/100“
, 10' were all set to 100. ) Table 1-6 As is clear from Table 1-6, the emulsion of the present invention has suppressed fog and has high sensitivity (especially at low illuminance).

Samples 1 to 16 coated with this emulsion were left in an environment of 25 DEG C. and 60% humidity for 12 months, and then subjected to exactly the same sensitometric experiment. Table 1-7 shows the results expressed in relative sensitivity, with the sensitivity of sample 1 before aging being 100. It can be seen that the coated samples of the emulsions of the present invention showed excellent storage stability with little decrease in sensitivity and little increase in fog over time.

Similar experiments were conducted with ascorbic acid compounds other than L-ascorbic acid, and it was confirmed that they exhibited excellent photographic performance similar to L-ascorbic acid.

Table 1-7 Example 2 In the step of forming an emulsion according to the same emulsion preparation method as in Example 1, reduction sensitizers such as tin chloride and thiourea dioxide were added 1 minute after the start of shell formation, and E m -■, Em - An IV was prepared. The amount of the reduction sensitizer used here was adjusted so that a sensitivity of 1/100" would be optimal when chemical sensitization and spectral sensitization were performed later.

Table 2-1 was added and optimally gold-sulfur sensitized using chloroauric acid and sodium thiosulfate. At this time, when 70% of the chemical sensitization was completed, reduction sensitization was performed by adding tin chloride or thiourea dioxide to prepare emulsions VI-3 and Vl-4. The amount of reducing agent added at this time was emulsion Vl-1,
■-・I added almost all of my colleagues as in 2.

Table 2-2 Using this emulsion, the same dye (1) as in Example 1 was added at 3 x 10-' mol per 1 mol of Yiran before the start of chemical sensitization, and 60
Emulsions V[-1 and Vl-2 were prepared which were optimally sensitized with gold and sulfur using chloroauric acid and sodium thiosulfate at .degree.

Furthermore, a spectral sensitizing dye was applied to the unchemically sensitized emulsion prepared in Example 1 before the start of chemical sensitization, and a coated sample was prepared in the same manner as in Example 1 using this emulsion, and a sensitometric experiment was conducted. The tests were carried out immediately after application and after 12 days of menstruation at a temperature of 25° C. and a humidity of 60%.

The results show that the sensitivity of coating sample 1-1 in Example 1 is 1O#1/1.
When both 00' and 100 were used, the relative sensitivity was expressed immediately after coating.

Table 2-3 (Immediately after application) (After 12 days of menstruation) It is clear that reduction sensitization using substances other than ascorbic acid has high fog and that fog increases and sensitivity decreases significantly over natural aging.

Example 3 On a subbed cellulose triacetate film support,
A sample of a multilayer color light-sensitive material was prepared by coating layers having the compositions shown below.

(Photosensitive layer composition) The numbers corresponding to each component indicate the coating amount expressed in g/cd, and for silver halide, the coating amount is expressed in terms of silver.However, for sensitizing dyes, the halogen in the same layer The coating amount is expressed in moles per 1 mole of chemical compound.

Sample 1st layer; antihalation layer black colloidal silver silver 0.18 gelatin
0.40 Second layer; Middle layer 2.5-di-t-pentadecylhydroquinone 0.18EX-10
,07 EX-30,02 EX-120,002 U-10,06 U-20,08 U-30,10 HBS-10,10 HBS-20,02 Gelatin 1.04 Third layer (first red emulsion layer) Monodisperse silver iodobromide emulsion (iodide! I6 mol%, average grain size 0.6μ, coefficient of variation regarding grain size 0°15)
Silver 0o55 Sensitizing Dye 1 6.9X10-' Sensitizing Dye■ 1.8X10-' Sensitizing Dye III
3. lXl0-'sensitizing dye IV
4.0X10-'EX-20,350 8BS-10,00S EX-100,020 Gelatin l・20 4th layer (
2nd red-sensitive emulsion layer) Tabular silver iodobromide emulsion (silver iodide 10 mol%, average aspect ratio 5.5, silver 1.0 5.1X10-'1.4X10-'2.3X10-' 3. 0X10-' 0.400 o, os.

O,015 1,30 Average particle size 0.7μ, average thickness 0.2μ) Aggravating pigment! Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ EX-2 EX-3 EX-10 Gelatin 5th layer (third red-sensitive emulsion layer) Silver iodobromide emulsion i EX-3 EX-4 BS-1 B5- 2 Gelatin 6th layer (middle layer) EX-5 BS-1 11i1.60 0.240 0.120 0, 22 0, 10 1, 63 0.040 0.020 Gelatin 0.80 7th layer (first green Sensitive emulsion layer) Tabular silver iodobromide emulsion (silver iodide 6 mol%, average grain size 0)
．． 6μ, average aspect ratio 6.0, average thickness 0.15)
Silver 0.40 sensitizing dye V
3.0X10-'sensitizing dye Vl 1.
0xlO-'sensitizing dye ■ 3.8xlO
-'EX-60,260 2X-10,021 EX-70,030 EX-80,025 HBS-10,100 HBS-40゜010 Gelatin 0.75 8th layer (second green-sensitive emulsion layer) Monodisperse iodine Silver bromide emulsion (silver iodide 9 mol%, average grain size 0)
．． 7μ, coefficient of variation regarding particle size 0°18)
Silver 0,80 sensitizing dye V2
．． lX10-' Sensitizing dye Vl 7.0
X10"' Sensitizing dye ■ 2.6X10-
'EX-60,180 EX-80,010 EX-10,008 EX-70,012 HBS-10,160 HBS-40,008 Gelatin 0.10 9th layer (3rd)! Sensitive emulsion layer) Silver iodobromide emulsion ■ Silver 1,2EX-60,
065 EX-110,030 EX-10,025 HBS-10,25 HBS-20,10 Gelatin 1.74 10th layer (
Yellow filter layer) Yellow colloid girl! 10.05EX-5
0,08 HBS-30,03 Gelatin 0.95 No. 11N (
1st blue emulsion layer) Tabular silver iodobromide emulsion (silver iodide 6 mol%, average grain size 0)
．． 6μ, average aspect ratio 5.7, average thickness 0.15)
Silver 0,24 sensitizing dye ■ 3
．． 5X10-'EX-90,8S EX-80,12 HBS-10,28 Gelatin 1/28 12th layer (second blue-sensitive emulsion layer) Monodispersed silver iodobromide emulsion (silver iodide 10 mol%, average grain Diameter 0.8μ, coefficient of variation regarding particle size 0.16>
Silver 0.45 sensitizing dye ■ 2.
lX10-'EX-90,20 EX-1o 0.015HBS
-10,03 Gelatin 0.46 13th layer (
Third blue-sensitive emulsion layer) Silver iodobromide emulsion ■ Silver 0.77EX-90
゜20 HBS-10,07 Gelatin 0.69 14th layer (
1st protective layer) Silver iodobromide emulsion (iodide 111 mol%, average grain size 0,
07 μ) tl
o, 5U-40,11 0-50,17 8BS-10,90 Gelatin 1.00 15th layer (
2nd protective layer) Polymethyl acrylate particles (diameter approximately 1.5 μm) 0.543-1
0.153-2
0.05 gelatin
0.72 In addition to the above components, gelatin hardening agent H-1 and a surfactant were added to each layer.

U-2 0■ X-1 (i)CJqOCONH EX-8 EX CH.

Hx EX-10 EX-11 EX-12 H-1 tHs Js CHt =Cl1 Sow CfhCOHHCH□
CHz=CHSOx CHg-C0NH-CI snow sensitizing dye HB S -1 B5-2 B5-3 B5-4 Tricresyl phosphate diptylphthalate bis(2-ethylexyl) phthalate■ (CHg)isOJa (CHz)*S (h.

(CH zsO, Na dls Dye group l (red-sensing dye) Cz It s Dye group 2 (green-sensing dye) Dye group 3 (blue-sensing dye) Sensitizing dye ■ 2.2 x 10-' mol 1 mol Ag 5th layer Silver iodobromide emulsion I, 9th N silver iodobromide emulsion ■, 1st
Samples 301 to 304 were prepared in the same manner except that the three-layer silver iodobromide emulsion (2) was changed.

These samples were exposed to light for sensitometry, and then subjected to the following color development process.

The concentration of the treated sample was measured using a red filter, a green filter, and a blue filter. The results obtained are shown in Table 3-3.

Regarding the results of photographic performance, the sensitivities of the red-sensitive layer, green-sensitive layer, and blue-sensitive layer were each expressed as relative sensitivities when the sensitivity of sample 301 was taken as 100.

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

Color development 3 minutes 15 seconds Bleach White 6 minutes 30 seconds Water wash 2 minutes 10 seconds Fixed arrival time: 4 minutes 20 seconds Water washing 3 minutes 15 seconds Stability 1 minute 05 seconds The composition of the treatment liquid used in each step was as follows.

Color developer diethylenetriaminepentaacetic acid 1.0g 1-hydroxyethylidene-1,1-diphosphonic acid 2.0g sodium sulfite 4.0g potassium carbonate
30.0g Potassium bromide Potassium iodide Hydroxylamine sulfate 4-(N-ethyl-N-β-hydroxyethylamino)-2-methylaniline sulfate Add H bleach solution Ethylenediaminetetraacetic acid ferric ammonium salt Ethylenediamine Disodium Tetraacetic Acid Salt Ammonium Bromide Ammonium Nitrate Add water and H Fixer Ethylenediamine Tetraacetic acid Disodium 1,4g 1,3■ 2,4g 4,5g 1, OR 10,0 +00゜0g 10.0g 50.0g 10 .0g 1, 0 7! 6.0 Thorium salt 1.0g Sodium sulfite 4.0g Ammonium 1000sulfate aqueous solution (70%> 175.0g Sodium bisulfite 4.6g Add water
l・θ' pH 6,6 Stabilized liquid formalin (40%) 2.0d Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) Add 0.3g water 1.01 Iodobromide used here Silver emulsions I, ■, and ■ were prepared as follows.

Using the unchemically sensitized emulsion Em-1 of Example I, adding spectral sensitizing dye groups 1 and 2.3 according to dye addition method A,
Emulsions R-1 and G using silver chloride and sodium thiosulfate
-1 and B-1 were produced.

Spectral sensitizing dye group 1.2.3 was added using Em-1 according to dye addition method C, and chemically sensitized optimally in the same manner as emulsion R-1, etc., so that 70% of the chemical sensitization process was performed. Emulsions R2, G-2, and B-2 were prepared by adding 2 x 10-' mol of L-ascorbic acid compound at the time of the addition.

Using Em-1 and following dye addition method A, emulsions R3, G-3, and B-3 were obtained by performing gold/sulfur sensitization and reduction sensitization with L-ascorbic acid in the same manner as Emulsion R-2. was created.

Spectral sensitization, chemical sensitization, and L-ascorbic acid were carried out in the same manner as Emulsion 1'13, etc., except that Em-1 was used and a thiosulfonic acid compound was added at 3X10-' mol per 1 mol of iff before the start of chemical sensitization. Emulsion R subjected to reduction sensitization by
-4, G-4, and B-4 were produced.

Table 3-1 Table 3-2 Using this, multilayer tofu samples 301 to 304 were produced.

Table-3-3 (continued) R indicates red sensitivity, G indicates green sensitivity, and B indicates blue sensitivity.

Incidentally, fog is the value obtained by subtracting the original fixing density.

As is clear from Table 3-1, it can be seen that the emulsion of the present invention has the effect of increasing sensitivity with almost no increase in fog.

Further, when the photographic performance after aging was examined in the same manner as in Example 1, it was found that the samples using the emulsion of the present invention exhibited good storage stability.

Example 4 Samples 301 to 303 of the present invention were exposed in the same manner as in Example 3, and then processed using an automatic processor according to the method described below.

Processing method Process Processing time Color development 3 minutes 15 seconds Bleach White 1 minute 00 seconds Bleach fixing 3 minutes 15 seconds Washing with water (1140 seconds Washing with water (2) 1 minute 00 seconds Stability 40 seconds Drying 1 minute 15 seconds Next, the composition of the treatment liquid will be described.

(Color developer) Processing temperature 38°C 38°C 38°C 35°C 35°C 38°C 55°C Diethylenetriaminepentaacetic acid l-hydroxyethylidene-1,1-diphosphonic acid Sodium sulfite Potassium carbonate Potassium bromide Potassium iodide Hydroxylamine sulfur M salt (Unit g) 1,0 4-[N-Ethyl-N-(β-hydroxyethyl)aminoco-2-methylaniline sulfate solution is added to pH (Bleach solution) Ethylenediaminetetraacetic acid ferric ammonium dihydrate Ethylenediaminetetraacetic acid Disodium acetate Salt Ammonium Bromide Ammonium Nitrate Bleach accelerator Aqueous ammonia (27%) Add water H (bleach-fix solution) 4.5 1,0! 10.05 (Unit g) l 20°10, 0 100.0 10, O O,005 mol 15.0s + ff1 1,01 6.3 (Unit g) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 50. O ethylenediaminetetraacetic acid disodium salt 5. 0 Sodium sulfite 12.0 Ammonium osulfate aqueous solution (70%) 240.0 mf ammonia water (27%) Add 6.0 ml of water to pH 1.01 pH 7.2 (Washing liquid) Add tap water to H-type strongly acidic cation exchange resin ( Water is passed through a mixed bed column packed with Amberlite IR-120B (manufactured by Rohm and Haas) and an OH-type anion exchange resin (Amberlite IR-400) to reduce the concentration of calcium and magnesium ions to 3/1 or less. This was followed by the addition of 20 g/.beta. of sodium isocyanurate dichloride and 1.5 g/l of sodium sulfate. The pH of this solution is 6.5-7
It is in the range of ゜5.

(Stabilizing liquid) (Unit g) Formalin (37%) 2.0d Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 Ethylenediaminetetraacetic acid disodium salt 0.05 Add water 1. 01 pH 5.0-8.0 Samples 301 to 303 of the present invention had good results as in Example 3 even after this treatment.

Example 5 Samples 301 to 303 of the present invention were exposed in the same manner as in Example 3, and then processed by the method described below using an automatic processor.

Processing method Process Processing time Processing temperature Color development 2 minutes 30 seconds 40℃ Bleach fixing 3 minutes 00 seconds 40℃ Wash with water ill for 20 seconds at 35℃ Washing f2＞　　　　20 seconds Stable 20 seconds Dry 50 seconds Next, the composition of the treatment liquid will be described.

(Color developer) Diethylenetriaminepentaacetic acid ■-Hydroxyethylidene-1,1-diphosphonic acid Sodium sulfite Potassium carbonate Potassium bromide Potassium iodide Hydroxylamine sulfate 4-(N-ethyl-N-(β-hydroxyethyl) aminoco- Add 2-methylaniline sulfate solution H (bleach-fix solution) 35°C 35°C 65°C (unit g) 2.0 4.5 1, θ 1 10.05 (unit g) Ferric ammonium ethylenediaminetetraacetate Water salt Ethylenediaminetetraacetic acid disodium salt Sodium sulfite ammonium thiosulfate aqueous solution (70%) Nitric acid (98%) Bleach accelerator 50,0 5.0 12,0 260.0d 5,0- Add 0.01 mol water 1 .0Ep+(6
,0 (Washing liquid) A mixed bed column filled with tap water and an H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and an OH-type anion exchange resin (Amberlite IR-400 manufactured by Rohm and Haas) The calcium and magnesium ion concentrations were reduced to below 3/I by passing water through the solution, followed by adding 20/I of sodium isocyanurate dichloride and 1.1/I of sodium sulfate. 5g/It was added.

The pH of this liquid is in the range of 6.5 to 7.5.

(Stabilizing solution) (Unit: g) Formalin (37%) 2. (ld polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 ethylenediaminetetraacetic acid disodium salt 0.05 water added
1.01 pH 5.0-8.0 Samples 301 to 303 of the present invention had good results as in Example 4 even after this treatment.

Example 6 On a subbed cellulose triacetate film support,
A sample of a multilayer color photosensitive material consisting of each layer having the composition shown below was prepared.

(Composition of photosensitive layer) The coating amount is expressed in units of g/ld of silver for silver halide, colloidal silver, and couplers, and the number of moles per at mole of halide in the same layer for sensitizing dyes. Indicated.

1st N: Antihalation layer black colloidal silver silver coated M O12 gelatin
2.20V-10,I LJV-20,2 Cpa-1o,os Solv-10,01 Solv-20,01 Solv-30,08 2nd layer: Intermediate layer fine grain silver bromide (equivalent sphere diameter 0.07μ) Silver coating no, ts Gelatin 1.0Cpcl-2
o, 2 Third layer: First red-sensitive emulsion layer Silver iodobromide emulsion (AglIO, 0 mol%, internal high Agl type, equivalent sphere diameter 0.7 μ, coefficient of variation of equivalent sphere diameter 14%, 14
Hedron particles) Daughter application! E O,26 Silver iodobromide emulsion (Ag! 4.0 mol%, internal high Agl type,
Equivalent sphere diameter 0.4μ, coefficient of variation of equivalent sphere diameter 22%, tetradecahedral particles) Silver coating amount 0.2 Gelatin 1. 0E xS-
14,5X10-'molExS-21,5xlO-'molExS-30,4xlO-'molExS-40,3xlO-'truExC-10.33 ExC-20,009 ExC-30,023 ExC-60, 14 4th layer: 2nd red-sensitive emulsion layer Silver iodobromide emulsion (Ag 116 mol%, internal high AgI type, equivalent sphere diameter 1.0μ, coefficient of variation of equivalent sphere diameter 25%, plate-like grains, diameter/W- Ratio 4.0) Silver coating amount 0°55 Gelatin 0.7ExS-13
X10-'ExS-21xto-'ExS-30,3xio-'BxS-40,3xto-' ExC-30,05 EXC-40,10 ExC-60,08 5th layer: 3rd red-sensitive emulsion layer iodobromide Silver emulsion! (Internal muscle Agl type, ball equivalent diameter 1°2μ
, coefficient of variation of equivalent sphere diameter 28%) Silver coating amount Gelatin ExC-4 ExC-5 Solv-I Solv-'1 6th layer: Intermediate layer gelatin 1.0 Cpd-40,1 7th layer: First green feeling Emulsion layer Silver iodobromide emulsion (Agl 10.0 mol%, internal streak Agl type, equivalent sphere diameter 0.7 μ, coefficient of variation of equivalent sphere diameter 14%, 14
Silver coated I O12 Silver iodobromide emulsion (Ag + 4.0 mol%, internal streaks Agl type,
Equivalent sphere diameter 0.4μ, coefficient of variation of equivalent sphere diameter 22%, tetradecahedral particles) Silver coating amount 0.1 1.2 sxto-'2X10-'1xio-' 0,41 0, l 0 0, 03 0. 2 0, 03 Gelatin xS-5 xS-6 High iodine type, equivalent sphere diameter 1.0μ, coefficient of variation of equivalent sphere diameter 25%, plate-like particles, diameter/thickness ratio 3.0) Silver coating amount 0.4 Gelatin 0.35ExS-5
3,5xto-'ExS-61,4xto-'ExS-70,7X10-' ExM-10,09 ExM-30,01 Solv-10,15 Solv-50,03 9th layer: Intermediate layer gelatin 0.5th layer 10th layer: 3rd green-sensitive emulsion layer Silver iodobromide emulsion ■ (internal streak Agl type, equivalent sphere diameter 1° 2μ,
Coefficient of variation of equivalent sphere diameter 28%) Silver coating amount 1.0 Gelatin 0.8ExM-3
0,01 ExM-40,04 ExC-40,005 Solv-10,2 11th layer: Yellow filter layer Cpd-3o,05 Gelatin 0.5Solv-1
0,1 12th layer: Intermediate layer gelatin 0. 5Cpd-2
0,1 13th layer: First blue-sensitive emulsion layer Silver iodobromide emulsion (Ag [10 mol%, internal high iodine type, equivalent sphere diameter 0.7 μ, coefficient of variation of equivalent sphere diameter 14%, tetradecahedral grains) Silver coating amount 0. 1 Silver iodobromide emulsion (Ag + 4.0 mol%, internal high iodine type,
(equivalent sphere diameter 0.4 μ, coefficient of variation of equivalent sphere diameter 22%, tetradecahedral particles) Silver coating amount 0.05 Gelatin 1. 0ExS-8
3xlO~4 ExY-10,53 ExY-20,02 Solv-10,15 14th layer: 2nd blue-sensitive emulsion layer Silver iodobromide emulsion (Ag119.0 mol%, inner cylinder Agl type, equivalent sphere diameter 1. 0μ, coefficient of variation of equivalent sphere diameter 16%, 14
Face piece particles) Silver coating amount 0.19 Gelatin 0. 3ExS-8
2X10-' ExY-10,22 Solv-10,07 15th layer: Intermediate layer fine grain silver iodobromide (Ag 12 mol%, uniform type, equivalent sphere diameter 0
．． 13μ) Silver coating amount 0.2 Gelatin 0.36 16th layer:
Third blue-sensitive emulsion layer Silver iodobromide emulsion m (inner cylinder Agl type, equivalent sphere diameter l.

2μ, coefficient of variation of equivalent sphere diameter 28%) Silver coating amount 1, O Gelatin 0.5ExY-10,
2 Solv-10,07 17th layer: 1st protective layer gelatin 1°UV-10°UV-20°5olv-10°5olv-20°18th layer: 2nd protective layer Fine particle bromide 11 (equivalent sphere diameter 0 .07μ) Silver coating amount
0.18 Gelatin 0.7 Polymethyl methacrylate particles (diameter 1.5 μ) 0.2 W-10,02 H-10,4 Cpd-51,0 ExC-1 (i) CaHJCOCNtl ExC-2 Hz ExC -3 xM l1ff l xM ExC-6 H (i)CJvOCONH OCL(:IIzSC1l□Cool xC-4 0]1 (i)CJ*0CNII ■QC)1. CII□5CIICOOH (b)C+Jzs ExC-5 H OCHzCHzSCIICOOH C+zll□.

xM-4 l xM-5 ExY-1 ExY xS-1 xS xS-8 olv-1 ZH5 xS-3 olv-2 0IV-3 olv-4 olv-5 pd-1 Js Cz Ifs Cpd-2 Cpd-3 Cpd-4 Cpd-5 (ExS-7 8X10-'mol dye group 3 ExS-8 sxio-’mol Using this, multilayer tofu samples 601 to 604 were produced.

CaF, SO! NHCHICHICH,0CI1. cl
! N(CH3) 3CH* = CHS Oz CHt
CON HCHzCHt = CHS OzCHt
CON H-CHZ The emulsions used here are dye groups 1 (red sensibility), 2 (green sensibility), and 3 (blue sensibility) of Example 3.
Emulsion R1 was prepared in exactly the same manner as the emulsion preparation method of Example 3, except that dye groups 1', 2', and 3' were changed to dye groups 1', 2', and 3' shown below.
', c-i'...B-4'' was prepared and used.

Dye group 1' per 111 moles Dye group 2' Same as each sample except that the silver iodobromide emulsion ■ in the 5th layer, the silver iodobromide emulsion ■ in the 1st O layer, and the silver iodobromide emulsion ■ in the 16th layer were changed. Samples 601 to 604 were prepared in this manner.

These samples were incubated at 40°C and 70% relative humidity for 14 days.
After standing for a period of time, exposure for sensitometry was applied, and the same color development process as in Example 3 was performed.

The concentration of the treated sample was measured using a red filter, a green filter, and a blue filter. The results obtained are shown in Table 6-3.

Regarding the results of photographic performance, the sensitivities of the red-sensitive layer, green-sensitive layer, and blue-sensitive layer were each expressed as relative sensitivities when the sensitivity of sample 601 was taken as lOO.

As is clear from Table 6-3, it can be seen that the emulsions of the present invention have the effect of increasing sensitivity with almost no increase in capri.

Further, when this sample was aged in the same manner as in Example 1 and then examined for photographic performance, it was found that the sample using the emulsion of the present invention exhibited good photographic performance.

Table 6-2 Table-6-3 (continuation) Table-6 R indicates red sensitivity, G indicates green sensitivity, and B indicates blue sensitivity.

Incidentally, fog is the value obtained by subtracting the original fixing density.

Example 7 On a subbed cellulose triacetate film support,
Samples 701 to 704, which are multilayer color photosensitive materials each having each layer having the composition shown below, were prepared.

(Composition of photosensitive layer) The coating amount is expressed in g/cd of silver for silver halide and colloidal silver, and the amount expressed in g/rd for coupler additives and gelatin. The number of moles of the dye is expressed per mole of silver halide in the same layer. Note that the symbols indicating additives have the meanings shown below. However, if a substance has multiple effects, one of them is listed as a representative.

LIV, ultraviolet absorber, 5OIVS high boiling point organic solvent, E
XF: dye, ExS: sensitizing dye, ExCi cyan coupler, EXMi magenta coupler ExY: yellow coupler, cpaH additive 1st layer (antihalation layer) black colloidal silver 0.15 gelatin 2.9UV-10,03 UV-20 ,06 UV-30,07 Solv-20,08 ExF-10,01 ExF-20,01 2nd layer (low-sensitivity red-sensitive emulsion Ji) Silver iodobromide emulsion (Ag 14 mol%, uniform, equivalent sphere diameter 0. 4
μ, coefficient of variation of equivalent sphere diameter 37%, plate-like particles, diameter/thickness ratio 3.0) Coated silver amount 0.4 Gelatin 0.8xS-1 ExS-2 ExS-5 ExS-7 ExC-1 ExC-2 ExC-3 3rd layer (mid-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (Ag 16 mol%, internal type Ag f with a core-shell ratio of 2:1, equivalent sphere diameter 0.65μ, coefficient of variation of equivalent sphere diameter 25%) , plate-shaped grain, diameter/thickness ratio 2.0) 3 X 1 0-' 4 X 1 0-'3X10-' O Emulsion (Ag 14 mol%, uniform Agl type, equivalent sphere diameter 0.4μ, coefficient of variation of equivalent sphere diameter 37%, plate-like grains, diameter/thickness ratio 3.0) Coated silver amount 0. 1 Gelatin 1.0ExS-12
xlO-'ExS-21,2X10-'ExS-5zxto-'ExS-77X10-' ExC-10,31 BxC-20,01 ExC-30,06 4th layer (high sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion! (Internal height Agl with core shell ratio 1:2
(type, equivalent ball diameter 0.75 μ, coefficient of variation of equivalent ball diameter 25%)
Coated silver amount 0. 9 Zeradin
0. 8ExC-10,07 ExC-40,05 Solv-10,07 Solv 2 0.20Cpd-
74,5xto-' 5th layer (middle layer) Gelatin 0.6UV-40,
03 UV-50,04 cpa-t O.1 polyethyl acrylate latex 0.08Solv-
10,05 6th layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (Ag 14 mol% uniform type 0 sphere equivalent diameter 0.4
μ, equivalent sphere diameter 0.7 μ, coefficient of variation of equivalent sphere diameter 37%, plate-like particles, diameter/thickness ratio 2.0) Coated silver amount
0.18 gelatin 0.4Ex
S-32X1 (I'ExS-47xio-'ExS-5txto-' ExM-50,11 ExM-70,03 ExY-80,01 Solv-10,09 Solv-40,Of 7th layer (medium-sensitivity green-sensitive emulsion Layer) Silver iodobromide emulsion (Ag 14 mol%, core-shell ratio 1:1 surface height Agr type, legal equivalent type, equivalent sphere diameter 0.5μ, coefficient of variation of equivalent sphere diameter 20%, plate-like grains, diameter/thickness Ratio 4.0) Coated silver amount 0.27 Gelatin 0.6ExS-32
X10-' ExS-47 Silver bromide emulsion ■ (internal high Agl type with core-shell ratio 1:2, equivalent sphere diameter 0.75μ, coefficient of variation of equivalent sphere diameter 25%)
Application amount 0.7 gelatin
0. 8ExM-50,I ExM-60,03 ExY-80,02 ExC-10,02 ExC-40,01 Solv-10,25 Solv-20,06 Solv-40,01 Cpd-71XIO-' 9th N (intermediate layer ) Gelatin 0. 6Cpd-1
0.04 Polyethyl acrylate latex 0.12Solv-
L 0.02 10th layer (donor N for interlayer effect on red-sensitive layer) Silver iodobromide emulsion (Ag16
Mol%, internal high Agl type with core-shell ratio 2:l, equivalent sphere diameter 0.7 μ, coefficient of variation of equivalent sphere diameter 25%, plate-shaped particles, diameter/thickness ratio 2.0) Coated silver amount 0.68 iodine Kagen emulsion (Ag 14 mol% uniform type, coefficient of variation of equivalent sphere diameter 37
%, plate-shaped particles, diameter/thickness ratio 3.0) Coated silver 1 0.19 Gelatin 1.
0ExS-35xto-' ExM-100,19 Solv-10,20 11th layer (yellow filter layer) Yellow colloidal silver 0.06 gelatin 0.8Cpd-20,13 Solv-10,13 Cpd-1o, 07 Cpd-60 ,002 H-10,13 12th layer (low sensitivity blue-sensitive emulsion N) Silver iodobromide emulsion (Ag 14.5 mol%, uniform Agl type, equivalent sphere diameter 0.7 μ, coefficient of variation of equivalent sphere diameter 15% , plate-shaped grains, diameter/thickness ratio 7.0) Coated silver 10.3 Silver iodobromide emulsion (Ag 13 mol%, uniform-Agl type, equivalent sphere diameter 0.3μ, coefficient of variation of equivalent sphere diameter 30%, plate shaped particles, diameter/thickness ratio 7.0) Coated silver 1 0.15 Gelatin 1.8ExS-69
X10-' ExC-10,06 ExC-40,03 ExY-90,14 ExY-110,89 Solv-10,42 13th layer (middle layer) Gelatin 0.7ExY-12
0,20 Solv-10,34 14th layer (high sensitivity blue-sensitive emulsion N) Silver iodobromide emulsion ■ (core-shell ratio 1:2 internal high Agl type, equivalent sphere diameter 0.75μ, coefficient of variation of equivalent sphere diameter 25%)
Coated silver IO,5 gelatin
0.5ExY-90,01 ExY-110,20 ExC-10,02 Solv-10,10 15th layer (first protective layer) Fine grain silver bromide emulsion (Ag 12 mol%, uniform Agl type, equivalent sphere diameter 0 .07μ) Coated silver 1 0.12 Gelatin 0°9UV-40,
11 UV-50,16 Solv-50,02 8-10,13 cpct-5o, 10 Polyethyl acrylate latex 0.09 16th layer (second protective layer) Fine grain silver bromide emulsion (Ag 12 mol%, uniform -Agl type, equivalent sphere diameter 0.07μ) Coated silver amount 0.36 Gelatin 0.55 Polymethyl methacrylate particles Diameter 1.5μ 0. 2H-10,1
7 In addition to the above components, each layer contains emulsion stabilizer CPD-3 (
0,07g/rrr) Surfactant Cpd-4 (0,03
g/id) was added as a coating aid.

V-1 fhc CCHi C11゜ V-2 H Hs UV-3 HiCCCHs CH.

UV-4 Co-0-(:H3 (x / y = 7 / 3 weight ratio) N JV-5 o1v xF-1 3oIV　　　I olv-2 o1v-4 xS-1 xS-3 CH2 CH.

SO, Na SO2- ExS-5 co,=co.

5O1- ExS-6 ExS-7 5OsH・N(niz)Is)3 xC-3 H xC-4 0 ■ 1so-H*C*-0-Co-NH o-CHx-C1lz-3-CHx-COOHxS-8 xC-1 H NH-Co-0-C4H*-is.

lh xM-5 H3 Cj! xM-6 Ilff xM [SixM-10 xY pd pd-1 Il xY-8 XY-9 pd pd pd-5 N-dried N CH.

Cpd-3 Dye group l# Amount per mole of silver Cpd-4 H Dye group 2' In Em-1 of Example 1, the average equivalent sphere diameter of the seed crystal was set to 0.
．． 5 μm, so the average equivalent sphere diameter of the final particles is 0.75
Em-2Of is an emulsion prepared in the same manner as Em-1 of Example 1 except that the emulsion is μm.

f: For m-201, dye groups 1 (red feeling), 2 (green feeling), and 3 (blue feeling) of Example 3 were added to the following dye group 1.
Emulsions R-1#, G-1'...
......B-4# was prepared and used.

Dye group 3"
-3.

Regarding the results of photographic performance, the sensitivities of the red-sensitive layer, green-sensitive layer, and blue-sensitive layer were each expressed as relative sensitivities when the sensitivity of sample 701 was taken as 100.

Using this, multilayer tofu samples 701 to 704 were produced.

4th layer silver iodobromide emulsion ■, 8th layer silver iodobromide emulsion ■
, Sample 70 except that the 141st silver iodobromide emulsion ■ was changed.
Samples 702 to 704 were prepared in the same manner as in Example 1.

These samples were incubated at 40°C and 70% relative humidity for 14 days.
After standing for a period of time, exposure for sensitometry was applied, and the same color development process as in Example 5 was performed.

Treated samples with red filter and green filter Table-7-
3 (continued) R indicates red sensitivity, G indicates green sensitivity, and B indicates blue sensitivity.

Incidentally, fog is the value obtained by subtracting the original fixing density.

As is clear from Table 7-3, the color multilayer photosensitive material using the emulsion of the present invention has no increase in fog and has a clear effect of increasing sensitivity.

Further, when this sample was examined for photographic performance after storage over time in the same manner as in Example 1, it was confirmed that sample t1 of the present invention exhibited good photographic performance even after storage over time.

Procedural amendment 1゜ 2゜

Claims (3)

[Claims] (1) In the manufacturing process of silver halide emulsions, reduction sensitization is carried out with at least one kind of ascorbic acid or its derivatives, and chemical sensitization is carried out in the presence of a spectral sensitizing dye when chemically sensitizing the emulsion. A method for producing a distinctive silver halide emulsion. (2) 5 x 10^-^5 to 1 x per mole of silver halide
2. The method for producing a silver halide emulsion according to claim 1, wherein the reduction sensitization is carried out using 1 mole of ascorbic acid or a derivative thereof. (3) Claim (
The method for producing a silver halide emulsion as described in 1) or (2). [I) R-SO_2S-M [II] R-SO_2S-R^1 [III] R-SO_2S-Lm-SSO_2-R^2 In the formula, R, R^1, and R^2 may be the same or different. Often represents an aliphatic, aromatic, or heterocyclic group, M represents a cation, L represents a divalent linking group, and m is 0 or 1. The compounds of general formulas [I] to [III] may be polymers containing divalent groups derived from the structures represented by [I] to [III] as repeating units.