JPH02207239A - Production of photographic silver halide emulsion - Google Patents

Abstract

PURPOSE:To produce a photographic silver halide emulsion having high sensitivity and hardly causing fog by adding a specified amt. or more of a Pd compd. after a stage for forming particles and before a desalting stage. CONSTITUTION:A Pd. compd. is added by >=5X10<-5>mol per 1mol silver halide after a stage for forming particles and before a desalting stage. This addition means addition after the end of the addition of a silver salt soln. during the formation of particles and before the desalting stage. Namely, the Pd compd. may be added at the time when the addition of the silver salt soln. is finished or at an arbitrary time between the end of the addition of the silver salt soln. and the beginning of the desalting stage. All the Pd compd. may be added at once or the Pd compd. may be added in steps or may be continuously added for a prescribed time. A photographic silver halide emulsion having high sensitivity and hardly causing fog can be produced.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for producing a silver halide photographic emulsion. More specifically, the present invention relates to a stable method for producing a silver halide photographic emulsion with high sensitivity and low fog. In particular, the present invention relates to a stable method for producing silver halide photographic emulsions that are reduction sensitized in the grain forming step.

(Prior Art) US Pat. No. 2,448,060 discloses that sensitivity can be increased by adding a palladium compound and ascorbic acid to an emulsion after sulfur sensitization and before coating. U.S. Pat. No. 2,598,079 discloses that by adding a palladium compound to the emulsion after gold/sulfur sensitization and before coating, low-light sensitivity in particular can be increased. U.S. Patent No. 2.472,627, U.S. Patent No. 2.4
No. 72.631, No. 2,566.245 No. 2,566
．． No. 263 discloses that adding a palladium compound to an emulsion after chemical sensitization improves the storage stability of the sensitive material under high temperature and high humidity conditions.

British Patent No. 1,351,309 discloses adding 3.times.10@-7 to 3.times.10@-5 moles of a noble metal salt per mole of silver halide during the silver halide grain formation process (during conversion).

US Pat. No. 4,092,171 discloses that high sensitivity can be obtained and storage stability can be improved by adding an organic phosphinic acid complex of a palladium compound to an emulsion.

JP-A No. 61-67845 discloses monodispersed core/shell type silver halide grains in which the silver iodide content is different near the surface and inside the grains using a chalcogen sensitizer, a gold sensitizer, and a water-soluble palladium salt. Disclosed is a method for producing a silver halide emulsion which is chemically ripened in the presence of at least one of the following. Unexamined Japanese Patent Publication 1986
No. 212641 discloses that silver halide grains having (nnl) planes are chemically sensitized in the presence of a chalcogen sensitizer, a gold sensitizer, and a compound of a noble metal of group Ⅰ of the periodic table. \A method for producing a silver halogenide emulsion is disclosed.

On the other hand, JP-A-48-87825 discloses that by adding a reducing agent in the silver halide grain formation step, sensitivity is increased with a decrease in gradation. Japanese Patent Publication No. 58-1410 discloses that after adding a reducing agent in the silver halide grain formation process, an oxidizing agent is further added until the silver halide reaches its final size, thereby reducing the gradation. It is disclosed that the sensitivity increases without the accompanying increase in sensitivity. The effects of the present invention are particularly remarkable when applied to the above-mentioned emulsion in which a reducing agent and an oxidizing agent are sequentially added.

(Problems to be Solved by the Invention) An object of the present invention is to provide a method for producing a silver halogen photographic emulsion with high sensitivity and little fog.

Another object of the present invention is to provide a stable method for producing the above-mentioned silver halide photographic emulsion. In particular, it is an object of the present invention to provide a stable method for producing a silver halide photographic emulsion that is reduction sensitized during the grain formation process.

(Means for Solving the Problems) The above objects of the present invention were achieved by the following means. That is, this can be achieved by a method for producing a silver halide photographic emulsion, which is characterized in that a palladium compound is added in an amount of 5 Xl0-5 moles or more per mole of silver halide after the grain formation step and before the desalting step. Ta. In particular, after the grain formation process of reduction-sensitized silver halide grains in the grain formation process and before the desalting process, a palladium compound is added in an amount of 5X10-5 or more per mol of silver halide. This could be achieved by a method for producing silver oxide photographic emulsions.

The present invention will be explained in detail below.

The manufacturing process of silver halide emulsions is broadly divided into steps such as grain formation, desalting, chemical sensitization, and coating. Particle formation is nucleation,
It is subdivided into maturity, growth, etc. These steps are not carried out uniformly; chemical sensitization may be carried out simultaneously with particle formation, or chemical sensitization may be carried out repeatedly. Adding the palladium compound after the grain formation step and before the desalting step means adding the palladium compound at a time between after the addition of the silver salt solution in grain formation and before the desalting step. That is, it may be done at the same time as the addition of the silver salt solution is completed, or at any time after the addition of the silver salt solution is completed and before the desalting step. Even if the entire amount of palladium compound is added at once,
It may be added in several parts or continuously for a predetermined period of time. It may be aged after the addition of the palladium compound and before the desalting step, or it may be left at high temperature for a long time after the addition of the palladium compound and before the desalting step.

In the present invention, the palladium compound is added in an amount of 5×10 −' mol or more per mol of silver halide. Preferably lXl
Add up to 0-3 mol. Most preferably, the palladium compound contains at least 5 1X10-' moles per mole of silver halide.
Add up to X10-' moles.

If the amount is less than 1Xl0-5 mol, the effect of the present invention cannot be obtained, and if it is more than 10-3 mol, other problems will occur.

Here, palladium compound refers to palladium divalent salt or
It means salt of high value. Preferably the palladium compound is R2
It is represented by PdX6 or R2PdX4. Here, R represents a hydrogen atom, an alkali metal atom or an ammonium group. X represents a halogen atom, and represents a chlorine, bromine or iodine atom.

Specifically, 2PdCβ4+ (NH4)ZP d C
16°N a Z P d Cff 4 or (NH4
)zP d Cj! 4 is preferred. Pd(12, PdC
l! ,□ ・2 R20゜P d (NH:1)4Cz
2. (NH3)2P d Cl□, Pd1. .

Pd(OH)2. Pd (SO4), Pd
(NO3)2゜Na2Pd (NOzL or (NH,
1) Although zP d C1,s and the like may also be used, water-soluble palladium compounds are preferred. Most preferably, these palladium compounds are used in combination with thiocyanate ion in an amount of 5 times or more the mole of the palladium compound.

The conditions for adding the palladium compound are arbitrary. That is, the temperature may be 30°C or more and 80°C or less. Preferably 40
The temperature is not less than 70°C and not more than 70°C. Any values for pH, p, and Ag are allowed. Preferably the pH is 4 or more and 10 or less.

The most preferred embodiment of the present invention is to add the above-mentioned palladium compound after the formation of reduction-sensitized silver halide grains in the grain formation step and before the desalting step.

Applying reduction increase/decrease to the grain formation process of a silver halide emulsion basically means that it is performed during nucleation, ripening, and growth. Reduction sensitization may be carried out at any stage during nucleation, which is the initial stage of grain formation, during physical ripening, or during growth. The most preferred method is reduction sensitization during the growth of silver halide grains. Growing is a method in which reduction sensitization is performed while silver halide grains are growing by physical ripening or addition of a water-soluble silver salt and a water-soluble alkali halide. This means that it also includes a method in which reduction sensitization is performed in the same state and then further growth is performed.

The reduction sensitization of the present invention is a method of adding a known reducing agent to a silver halide emulsion, a method of growing or aging in an atmosphere with a low PAg of pA and g1 to 7, which is called silver ripening, and a method called high pH ripening. Either a method of growing in a high pH atmosphere of pH 8 to 11 or a method of aging can be selected. Moreover, two or more methods can also be used together.

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

As reduction sensitizers, stannous salts, amines and polyamines, hydrazine derivatives, formamidine sulfinic acid, silane compounds, poran compounds, etc. are known. In the present invention, a compound selected from these known compounds can be used, or two or more kinds of compounds can be used in combination. Preferred compounds as reduction sensitizers are stannous chloride, thiourea dioxide, and dimethylamine borane. The amount of the reduction sensitizer to be added depends on the emulsion manufacturing conditions and must be selected, but it is suitably in the range of 10@-8 to 10@-3 mol per mol of silver halide.

Reduction sensitizers include water, alcohols, glycols,
It can be dissolved in a solvent such as ketones, esters, amides, etc. and added during particle formation.

It may be added to the reaction vessel in advance, but it is preferable to add it at an appropriate time during particle formation. Alternatively, a reduction sensitizer may be added in advance to an aqueous solution of a water-soluble silver salt or a water-soluble alkali halide, and these aqueous solutions may be used to form particles. It is also a preferable method to add the reduction sensitizer solution in several parts or continuously as the particles are formed.

More preferably, the following general formula [■] is used in the production process of a reduction-sensitized silver halide emulsion.

At least one compound selected from the compounds represented by [■] and [■] is allowed to coexist.

R-3O2S-M [■] R-3O□S-R' CI) R3OzS-Lm-3SOz-R2 In the formula, R, R', and R2 may be the same or different,
It represents an aliphatic group, an aromatic group, or a heterocyclic group, and M represents a cation. L represents a divalent linking group, m is O or l
It is.

The compound of general formula CI) or III) may be a polymer containing a divalent group derived from the structure represented by [I) or I[[) as a repeating unit. Furthermore, when possible, R, R', R'', and L may be combined with each other to form a ring.

To explain the compounds of general formulas (1), (II) and [■] in more detail, when R, R' and R2 are aliphatic groups,
A saturated or lower chain, linear, branched or cyclic aliphatic hydrocarbon group, preferably an alkyl group having 1 to 22 carbon atoms, an alkenyl group or an alkynyl group having 2 to 22 carbon atoms, These may have a substituent. Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, hexadecyl, octadecyl, cyclohexyl, isopropyl, and naphthyl.

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 R2 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, piperidine, pyridine, tetrahydrofuran, thiophene, oxazole, thiazole,
Examples include imidazole, benzothiazole, benzoxazole, benzimidazole, selenazole, benzoselenazole, tetrazole, triazole, benzotriazole, tetrazole, oxadiazole, and thiadiazole ring.

Substituents for R, R' and R2 include, for example, alkyl groups (e.g. methyl, ethyl, hexyl), alkoxy groups (e.g. methoxy, ethoxy, 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 (
(e.g., phenylthio), acyl groups (e.g., acetyl, propionyl, butyryl, valeryl), sulfonyl!
(e.g. 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, -3025M group,
Examples include 5O2R' group.

The divalent linking group represented by is an atom or atomic group containing at least one selected from C, NS and 0. Specifically, alkylene group, alkenylene group, alkynylene group, arylene group, 0-, -3-, -NH-,
-CC)-, -3o□, etc. alone or in combination.

L is preferably a divalent aliphatic group or a divalent aromatic group. As the divalent aliphatic group of L, for example, +CHz element (
n = 1-12), CH2-CH=CH-CH2. Examples of the divalent aromatic group for L include a phenylene group and a naphthylene group.

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

M is preferably a metal ion or an organic cation.

Examples of metal ions include lithium ions, sodium ions, and potassium ions. Examples of organic cations include ammonium ions (eg, ammonium, tetramethylammonium, tetrabutylammonium), hostium ions (eg, tetraphenylphosphonium), and guanidyl groups.

When General 2 (1) to [■] are polymers, examples of repeating units include the following.

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

Specific examples of compounds represented by the general formulas CI), (I), or (1) are listed in Table A, but the invention is not limited thereto.

Compounds of general formula (1), (II) or (I) are disclosed in JP-A-54-1019; British Patent No. 972,211; Jo
urnal ofOrganic Chemistry
(Journal of Organic Chemistry) 53
Vol. 396 (1988) and Chemical Ab
Structs (Chemical Afstructs) 59
It can be easily synthesized by the method described or cited in Vol. 9766e.

The compound represented by the general formula CI), (II) or (III) has an amount of 10-7 to 10-1 per mole of silver halide.
Preferably, it is added in moles. Furthermore, 10 to 10-2,
Particularly preferred is an amount of 10-5 to 10-3 moles of Ag added.

In order to add the compound represented by general formula CI), (II) or (III) during the production process of a silver halide emulsion, a method commonly used when processing a photographic emulsion can be applied. For example, water-soluble compounds should be prepared in an aqueous solution with an appropriate concentration, and compounds that are insoluble or poorly soluble in water should be prepared in suitable organic solvents that are miscible with water, such as alcohols, glycols, ketones, esters, and amides. in,
It can be added as a solution by dissolving it in a solvent that does not adversely affect photographic properties.

The compound represented by compound (I), (II) or (I) may be added at any stage during the grain formation of the silver halide emulsion, before or after chemical sensitization. Preferred is a method in which the compound is added before or during reductive enhancement. In the present invention, it is preferable that the thiosulfonic acid compound is present during the silver halide grain formation step to carry out reduction sensitization.

Although the thiosulfonic acid compound of the present invention may be added to the reaction vessel in advance, it is preferable to add it at an appropriate time during particle formation. In addition, the compound [
1) to (III) may be added in advance and particles may be formed using these aqueous solutions. It is also a preferable method to add the solutions of compounds CI) to (In) in several portions or continuously over a long period of time as particles are formed.

The most preferred compound in the present invention is a compound represented by general formula (1).

The photographic emulsion used in the present invention includes silver bromide, silver iodobromide,
Any silver halide such as silver iodochlorobromide, silver chlorobromide, and silver chloride may be used. Preferred silver halides include silver iodobromide or silver chloroiodobromide, containing 30 mol% or less of silver iodide;
Silver bromide and silver chlorobromide.

The silver halide grains that can be used in the silver halide emulsion of the present invention include regular crystal grains that do not contain twin planes, as well as regular grains that do not contain twin planes.
Particles containing twin planes as explained in P, 163), such as single twins containing one twin plane, parallel multiple twins containing two or more parallel twin planes, and non-parallel twins. Depending on the purpose, it can be selected and used from non-parallel multiple twin crystals containing two or more planes. In the case of normal crystals, it is a cube consisting of (100) planes, an octahedron consisting of (111) planes, and the Tokko Kokko Sho 55-4.
Dodecahedral particles consisting of (110) planes disclosed in No. 2737 and JP-A No. 60-222842 can be used. Furthermore, Journal of Imaging
5science, Volume 30, Page 247, as reported in 1986, there are (hl)-plane particles with (211) as a representative, (hhl)-plane particles with (331) as a representative, (21)
Although (hko) plane particles representing the 0) plane and (hkl) plane particles representing the (321) plane require some ingenuity in their preparation methods, they can be selected and used depending on the purpose. A tetradecahedral particle in which (100) and (111) planes coexist in one particle, (
Particles with coexisting (100) and (110) planes or (1
11) Particles in which two or many surfaces 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 these silver halide grains may be fine grains of 0.1 micron or less, large grains with a projected area diameter of up to 10 microns, monodisperse emulsions with a narrow distribution, or polydisperse emulsions with a wide distribution. Even dispersed emulsions.

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 based on "Physics and Chemistry of Photography" by Grafkide, published by Paul Montell (P.
des, Chimie et Physique Ph
otographique Paul Montel,
1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G, F, DuffinPhotog)
rapic emulsion chemistry
(Focal Press.

1966), “Manufacture and Coating of Photographic Emulsions” by Zelikman et al.
, Published by Focal Press (V, L, Zelikman
etal, Making and Coating
Photographic EmulsionFoc
Al Press, 1964). i.e. acid method,
Any of the neutral method, ammonia method, etc. may be used, and the method for reacting the soluble root salt with the soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method, or a combination thereof. 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 one type of simultaneous mixing method, a method of keeping p and Ag constant in the liquid phase in which silver halide is produced, that is, a so-called Chondrald 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 p, Ag and pH during grain formation. For more information, please refer to Photographic Science and Engineering (Photography Science and Engineering).
c5science and engineering
) Volume 6, pp. 159-165 (1962), Journal of Photographic Science (Journa
l ofPhotograph fc 5science)
, Vol. 12, pp. 242-251 (1964), U.S. Patent No. 3,655,394 and British Patent No. L413,74.
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, Photography
yTheory and Practice (1930
), p. 131; Gutoff, Photographic Science and Engineering (Gutoff,
Photographic Science and E
ngineering), Vol. 14, p. 248, 257 (1970); U.S. Pat.
4.439520 and British Patent No. 2.112.1
It can be easily prepared by the method described in No. 57, etc. When tabular grains are used, the covering power increases;
Advantages include increased color sensitization efficiency with sensitizing dyes, and are detailed in the above-cited US Pat. No. 4,434,226.

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.

In the silver halide emulsion used in the present invention, the crystal structure of the silver halide grains may be --like, the inside and outside may have different halogen compositions, or they may have a layered structure. These emulsion grains are described in British patent no.
No. 027,146, U.S. Patent No. 3,505,068;
No. 4,444,877 and Japanese Patent Application No. 58248469
Disclosed in the issue etc. Furthermore, silver halides with different compositions may be joined by evitaxial joining (
, or may be bonded with a compound other than silver halide, such as silver rhodan or lead oxide.

The silver halide emulsion of the present invention preferably has a distribution or structure in terms of halogen composition in its grains.

Typical examples are JP-B No. 43-13162 and JP-A No. 6.
1-215540, JP-A No. 60-222845, JP-A No. 61-75337, etc., these are core-shell type or double structure type particles in which the inside and surface layers of the particles have different halogen compositions. 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 may be cubic or octahedral. Conversely, the core may be octahedral and the shelled particle may be cubic or octahedral. Furthermore, although the core part is a clearly regular particle, the shelled particle may be distorted or irregular in shape.

Moreover, it is not just a double structure, but also
It is possible to form a triple structure or a multilayer structure with more than that as disclosed in , or to apply a thin layer of silver halide having a different composition to the surface of a core-shell double structure grain.

In order to give a structure to the inside of a particle, it is not only possible to create a structure that envelops it as described above (it is also possible to create a particle that has a so-called bonding structure.
0, JP 58-108526, EP 199290
A2, JP 5814772, JP 59-1625
4, 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, non-silver salt compounds 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. The particles may have a low silveride content and a high shell portion. Similarly, grains having a bonded structure may be grains in which the host crystal has a high silver iodide content and the bonded crystal has a relatively low silver iodide content, 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 BP-009672
7B 1, EP-0064412B 1, etc., or DE2306447 C2, JP-A-60-22132.
Surface modification as disclosed in 0.0 may also be carried out.

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.

Silver halide solvents are useful to accelerate ripening. For example, it is known to have an excess of halogen 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 μ) components 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 emulsion is produced after the grain formation process (after precipitation or physical ripening), and after the palladium compound is added, soluble salts are removed (desalting process), which has been known for a long time. The Tardel water washing method, which is performed by gelatinizing gelatin, may be used, and inorganic salts consisting of polyvalent anions, such as sulfuric acid, anionic surfactants, anionic polymers (such as polystyrene sulfonic acid), or gelatin. A sedimentation method (flocculation) using a derivative (eg, aliphatic acylated gelatin, aromatic acylated gelatin, aromatic carbamoylated gelatin, etc.) may also be used.

The emulsion produced by the production method of the present invention is also chemically sensitized after the desalting step. Chemical sensitization is preferably carried out at 45°C or higher, more preferably at 50°C or higher. Preferably for 5 minutes or more,
More preferably, chemical sensitization is carried out for 10 minutes or more. In this chemical sensitization, active gelatin or a sulfur sensitization method using sulfur-containing compounds that can react with silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines); selenium sensitization method; reduction chemical substances (e.g. stannous salts, amines,
A reduction sensitization method using a hydrazine derivative, formamidine sulfinic acid, a silane compound); a noble metal sensitization method using a noble metal compound (complex salts of Pt and Ir in addition to total complex salts), etc. can be used alone or in combination. In this,
Preferably, chemical sensitization is performed by sulfur sensitization, selenium sensitization, or total complex salt sensitization alone or in combination.

Most preferred in the present invention is a combination of sulfur sensitization and gold sensitization (also referred to as gold/sulfur sensitization). Chemical sensitization is performed at pH 4 or above. Preferably pH
Performed at 5 or above.

Most preferably, a pH of 6 or higher, particularly 6.5 or higher, is effective for the present invention. The upper limit is 9 or less.

Preferably it is 8.5 or less.

Chemical sensitization is usually carried out with a PAg of 10 or more and 6 or more. Preferably, the number is 9 or more and 7 or more.

The photographic emulsion of the present invention and used in the present invention has the following properties: 1. To prevent fogging during the manufacturing process of the photosensitive abrasive material, during storage, or during photographic processing; Alternatively, various compounds can be included for the purpose of stabilizing photographic performance. That is, azoles, such as hengethiazolium salts, nitroindadules, nitrobenzimidazoles, chlorobenzimidazoles, promobenzimidazoles, mercaptodeazoles, mercaptobenzothiazoles, mercaptobenzimidazole necks, mercaptodeazoles,
Aminotriazoles, hengetriazoles, nitrobenztriazolina, mercaptothi-1-resols (especially l-phenyl-5-mercaptotetrazole), etc.; mercaptopyrimidines; mercaptotriazine, oxato compounds such as satrinthion; azaindene known as antifoggants or stabilizers, such as triazaindenes, teI-cyazaindenes (particularly 4-hydroxy-substituted (13,3a,7)tetraazaindenes), pentaazaindenes, etc. , many compounds can be added. For example, U.S. Patent 3,954
, No. 474, No. 3, No. 982, 947, Special Publication No. 1973
-28,660 can be used.

The photographic emulsions used in the present invention may be spectrally sensitized with methine dyes and others. The pigments used include cyanine pigments, merocyanine pigments, and ? ! Included are cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, sudyryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline nucleus, oxapurine nucleus, thiozoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus,
Pyridine nuclei, etc.; Nuclei in which an alicyclic hydrocarbon ring is fused to these nuclei; and nuclei in which aromatic hydrocarbon rings are fused to these nuclei, i.e., indolenine nucleus, henzindolenine nucleus, indole nucleus, benzoxane nucleus, etc. Dole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus, etc. are applicable. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, and a 2-thioxazolidine-2 nucleus having a ketomethylene structure.
, 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiobarbic acid nucleus, and the like can be applied.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.

Typical examples are U.S. Pat. Nos. 2,688,545 and 2,9
No. 77.229, No. 3,397,060, No. 3.52
No. 2.052, No. 3,527,641, No. 3,617
, No. 293, No. 3,628,964, No. 3,666.
No. 480, No. 3,672,898, No. 3,679,4
No. 28, No. 3,703,377, No. 3,769,30
No. 1, No. 3,814,609, No. 3,837,862
No. 4,026,707, British Patent No. 1,344,2
No. 81, No. 1.507, 803, Special Publication No. 43-493
No. 6, No. 53-12,375, JP-A-52-110,
No. 618 and No. 52-109.925.

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.

The dye may be added to the emulsion at any stage of emulsion preparation known to be useful.

It is most commonly carried out after chemical sensitization is completed and before application, but as described in U.S. Pat. No. 3,628,969 and U.S. Pat. Spectral sensitization can be carried out at the same time as chemical sensitization by adding it at the same time, or it can be carried out prior to chemical sensitization as described in JP-A-58113-928. It is also possible to start the spectral sensitization by adding it before the completion of the spectral sensitization. Furthermore, U.S. Patent No. 4,225
It is also possible to add these said compounds separately, i.e., some of these compounds are added prior to chemical sensitization and the rest are added after chemical sensitization, as taught in No. 666. Any time during silver halide grain formation is possible, including the method taught in U.S. Pat. No. 4,183,756.

The amount added is 4X10-6 to 1 per mole of silver halide.
Xl0-2 mol can be used, but when the silver halide grain size is 0.2 to 1.2 μm, about 5 x 10-5
~6X10-3 moles are more effective.

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.

For more information on these additives, please refer to Research Disclosure. -1tem 17643 (December 1978
) and 1 tem 18716 (1979,
(November), and the relevant sections are summarized in the table below.

Additive type ■ Chemical sensitizer 2 Sensitivity enhancer 4 Brightener Antifogging agent and stabilizer Antistain agent Dye image stabilizer Hardener Binder Plasticizer, lubricant Coating aid, Surface active agent 13 Static inhibitor RD17643 23 pages 24 pages 24-25 pages 25 right column 25 pages 26 pages 26 pages 27 pages 26-27 pages 27 pages RD18716 648 pages right column Same as above 649 pages right column 650 pages left-right column 651 pages left column Same as above page 650 right Column Same as above Same as above Various color couplers can be used in the photographic material of the present invention, and specific examples thereof are described in the patent described in Research Disclosure (RD) No. 17643, ■-〇-G mentioned above. has been done.

As a yellow coupler, for example, U.S. Patent Box 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,
1.476.760 is preferred.

As the magenta coupler, 5-pyrazolone and pyrazoloazole compounds are preferred, such as U.S. Pat.
, 310,619, 4,351,897, European Patent No. 73,636, U.S. Patent Box 3,061,432
No. 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-33552, Research Disclosure N
o, 24230 (June 1984), JP-A-60-4
No. 3659, U.S. Patent Box 4,500,630, U.S. Pat.
, 54 Hou No. 654 is particularly preferred.

Cyan couplers include phenolic and naphthol couplers, such as U.S. Patent Box 4,052,
No. 212, No. 4,146,396, No. 4,228
, No. 233, No. 4,296,200, No. 2,36
No. 9,929, No. 2.8OL171, No. 2.77
2.162, 2.895.826, 3 and 7
No. 72,002, No. 3,758,308, No. 4.
No. 334,011, No. 4,327,173, West German Patent Publication No. 3,329,729, European Patent No. 12L36
5A, U.S. Patent Box 3,446,622, U.S. Patent No. 4.3
No. 33.999, No. 4.451,559, No. 4,
427,767 and EP 161.626A are preferred.

Colored couplers for correcting unnecessary absorption of coloring dyes are available, for example, in Research Disclosure No. 17.
Section 643 ■-G, U.S. Patent Box 4,163,670,
Special Publication No. 57-39413, U.S. Patent Box 4,004,9
No. 29, No. 4,138,258, British Patent No. 1,1
46,368 is preferred.

Couplers whose coloring dyes have appropriate diffusivity include, for example, 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. 173, 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
No. 57-154234, No. 60184248,
Preferred are those described in US Pat. No. 4,248,962.

Couplers that release a nucleating agent or a development accelerator imagewise during development include, for example, British Patent No. 2,097.14.
No. 0, No. 2,13L188, JP-A-5915763
No. 8 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. Patent No. 4,130,427, and U.S. Pat.
No. 4,338,393, No. 4,310,61
Multi-dose coupler described in No. 8 etc., JP-A-60-1859
50, DIR redox compound or DIR coupler-releasing coupler described in JP-A No. 62-24252, etc., coupler releasing a dye that leaves a color after separation as described in European Patent No. 173.302A, R, D, No. 11449; Examples include bleach accelerator-releasing couplers described in JP-A No. 24241 and JP-A-61-201247, and ligand-releasing couplers described in US Pat. No. 4,553,477.

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 others.

The boiling point at normal pressure used in the oil-in-water dispersion method is 175°C.
Specific examples of the above-mentioned high boiling point organic solvents include phthalate esters (e.g., dibutyl phthalate, dicyclohexyl phthalate-1, di-2-ethylhexyl phthalate,
Decyl phthalate, bis(2,4-di-t-amylphenyl) phthalate, bis(2,4-di-amylphenyl) isophthalate, bis(LL-diethylpropyl) phthalate), phosphoric acid or phosphonic acid. Esters (e.g. triphel phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate and trichloropropyl phosphate, di2-ethylhexyl phenylphosphonate), benzoic acid esters (e.g., 2-ethylhexylhenscheid, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate), amides (
For example, N,N-diethyldodecaneamide, NN-diethyllaurylamide, N-tetradecylpyrrolidone),
Alcohols or phenols (e.g. isostearyl alcohol, 2,4-di-tert-amylphenol), aliphatic carboxylic acid esters (e.g. bis(2-ethylhexyl) sebaque 1-, dioctyl azelate, glycerol tributylphenol), isostearyl lactate, l-lioctyl citrate), aniline derivatives (e.g. N, N-dibutyl-2-butoxy-5
-tert-octylaniline), hydrocarbons (for example, paraffin, dodecylbenzene, diisopropylnafculene), and the like. In addition, as an auxiliary solvent, the boiling point is about 30°C or more, preferably about 50°C or more, about 160°C.
An organic solvent having a temperature of .degree. C. or lower can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide, and the like.

The steps and effects of latex dispersion methods and specific examples of latex for impregnation are described in U.S. Pat. ing.

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 that combine layer configurations and special color materials.

A typical example is illustrated below. JP 47-49031, JP 49-3843, JP 50-21248, JP 5158147, JP 59-60437, JP 60-227256, JP 61-4043 ,
As in JP-A-61-43743 and JP-A-61-42657, the coupling speed and diffusivity of color couplers are combined with the layer structure. Tokuko Sho 49-154
No. 95, 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. 53-3701
No. 7, Special Publication No. 53-37018, Japanese Patent Publication No. 51-490
No. 27, JP-A-52-143016, JP-A-53-9
No. 7424, JP-A-53-97831, JP-A-62-
200350 and JP-A No. 59-177551, which stipulate the arrangement of high-sensitivity layers and low-sensitivity layers and the arrangement of layers with different color sensitivities.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, No. 17643, page 28, and No. 1, 8
716, from the right column on page 647 to the left column on page 648.

The color photographic material according to the present invention includes the above-mentioned RD,
No. 17643, pages 28-29, and the same N.

18716, 651 left column to right column can be used for development processing.

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-NN-diethylaniline, 3-methyl- 4-amino-N-ethyl-Nβ
-Hydroxyethylaniline, 3-methyl4-amino-
N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-
Examples include methoxyethylaniline and their sulfates, hydrochlorides, p-toluenesulfonates, and the like. Two or more of these metal 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 antifoggants 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, organic solvents such as ethylene glycol, diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, fogging agents such as competing couplers sodium boron hydride, - Auxiliary developing agents such as phenyl-3-pyrazolidone, viscosity imparting agents, various chelating agents such as aminopolycarboxylic acid, aminopolybosphonic acid, alkylphosphonic acid, phosphonocarboxylic acid, etc. Acetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxydiiminodiacetic acid, 1-hydroxyethylidene-1,1
Diphosphonic acid, nitrilo-N, N, N-1-17 methylenephosphonic acid, ethylenediamine-N, N, N'
Representative examples include N'N thiramethylenephosphonic acid, ethylene glycol (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-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol. Alternatively, they can be used 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 current retaining solutions depends on the color photographic material to be processed, but in general, the amount of replenishment is 3! By reducing the bromide ion concentration in the replenisher,
It can also be less than A. When reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the area of contact with the air in the processing tank. Furthermore, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

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. Furthermore, in order to speed up the processing, a processing method may be used in which bleaching is followed by bleach-fixing. 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. Examples of bleaching agents include iron (■) and cobalt (II).
Compounds of polyvalent metals such as I), chromium (■), and copper (I[), peracids, quinones, nitro compounds, etc. are used.

Typical bleaching agents include ferricyanide; dichromate; organic complex salts of iron (II) or cobalt (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1.3- Aminopolycarboxylic acids such as diaminopropanetetraacetic acid, 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, iron(III) aminopolycarboxylate complexes and persulfates, including iron(III) ethylenediaminetetraacetate complexes, are preferred from the viewpoint of rapid processing and prevention of environmental pollution. Furthermore, aminopolycarboxylic acid iron(III) complexes are particularly useful in both bleach and bleach-fix solutions.

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

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 described in U.S. Pat. No. 3,893,858, German Pat.
, No. 290,812, No. 2,059,988, JP-A No. 5332, 736, No. 53-57,831, No. 53
-37,418, 5172.623, 53-9
No. 5,630, No. 53-95.631, No. 53-10
No. 4.232, No. 53-124, 424, No. 5314
Compounds having a mercapto group or a disulfide group as described in No. 1.623, No. 53-28,426, Research Disclosure +-NO, 17129 (July 1978); Thiazolidine derivatives described in Japanese Patent Publication No. 45-8506, Japanese Patent Publication Nos. 52-20,832 and 53-32,735, and U.S. Patent No. 3,706,561 Derivatives: West German Patent No. L127,715, JP-A-58-16,
Iodide salts described in No. 235; West German Patent No. 966.410
Polyoxyethylene compounds described in Japanese Patent Publication No. 2,748,430; Polyamine compounds described in Japanese Patent Publication No. 458836; Others 4142.434, 49-59
, No. 644, No. 53-94, No. 927, No. 54-35
, No. 727, No. 55-26, 506, No. 58-163
．． Compounds described in No. 940; bromide ions, etc. can be used.

Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and are particularly preferred, as described in US Pat. No. 3,893,858 and West German Patent No. 1,290,81.
No. 2, JP-A No. 51-95,630 is preferred. Also preferred are the compounds described in US Pat. No. 4,552,834. These bleach accelerators may be added to the photosensitive material. These bleach accelerators are particularly 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, with ammonium thiosulfate being the most widely used. Can be used for 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 washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, 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
our own of the 5ociety of
Motion Picture and Television
ision Engineers Volume 64, P, 2
48253 (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,
Calcium ions described in Japanese Patent Application No. 6113L632,
A method of reducing magnesium ions can be used very effectively. In addition, isothiazolone compounds and siaheradazoles described in JP-A No. 57-8,542,
Chlorine-based disinfectants such as chlorinated isocyanurate,
Others, such as benzotriazole, "Chemistry of antibacterial and antifungal agents" written by Hiroshi Horiguchi, "Sterilization of microorganisms, sterilization, and antifungal technology" edited by Sanitation Technology Society, "Dictionary of antibacterial and antifungal agents J" published by Japan Antibacterial and Antifungal Society. The fungicides mentioned can also be used.

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 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 30 seconds to 5 minutes at 25-40°C. A range is selected. Furthermore, the photosensitive 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
．． All known methods described in No. 834 and No. 60-220.345 can be used.

Further, following the water washing treatment, a further stabilization treatment may be carried out, such as a stabilizing bath containing formalin and a surfactant, which is used as a final bath for color photosensitive materials for photography. .

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

The overflow liquid resulting from the water washing and/or replenishment of the stabilizing liquid can also be reused in 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. In order to incorporate the color developing agent, it is preferable to use various precursors of the color developing agent. For example, U.S. Patent No. 3,342,59
Indoaniline compound described in No. 7, No. 3,342,
No. 599, Research Disclosure 14,850
No. 15,159, aldol compounds described in No. 13,924, U.S. Patent No. 3
, 719.492, JP-A-53-1
Examples include urethane compounds described in No. 35.628.

The silver halide color photographic material of the present invention may contain various 1-phenyl-3-
It is also possible to incorporate birapritons. Typical compounds are JP-A No. 56-64,339, JP-A No. 57144.547,
and No. 58-115,438.

Various treatment liquids in the present invention are used at 10°C to 50°C. Normally, a temperature of 33°C to 38°C is standard, but higher temperatures can be used to accelerate processing and shorten processing time, or lower temperatures can be used to improve image quality and stability of the processing solution. can be achieved. Further, in order to save silver on the photosensitive material, a treatment using cobalt intensification or hydrogen peroxide intensification as described in German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be carried out.

Furthermore, the silver halide photosensitive material of the present invention is disclosed in US Pat.
, 500, No. 626, JP-A-60-133449,
It can also be applied to the heat-developable photosensitive materials described in Japanese Patent No. 59218443, European Patent No. 61-238056, and European Patent No. 210,660A2.

(Example) Examples will be described below, but the present invention is not limited to these examples.

Example-1 The present invention will be explained while comparing it with a comparative example.

(Production method of Em-A) Aqueous solution 10 containing 40 g of gelatin and 2 g of KBro
The mixture was stirred vigorously at 75°C. Silver nitrate aqueous solution 2
03rd (AgNOz 1.46 g) and KBrBr aqueous solution were added over 2 8 g. After adjusting the silver potential of the reaction solution to -25 mV with respect to a saturated calomel electrode, thiourea dioxide was adjusted to 0. 6 mg was added as an aqueous solution. After that, 471 g of silver nitrate aqueous solution (A g NOs 9 4.2 g
) and KBr aqueous solution (KBr, 14.6 wt%) for 33 minutes at the same time, the flow rate of the silver nitrate aqueous solution was adjusted to an initial flow rate of 1 m
ft1 min, final flow rate 19rd/min, and the silver potential of the reaction solution was maintained at -25 mV. After the addition was completed, the mixture was aged for 10 minutes and then desalted by the flocculation method. Add 43 g of gelatin and bring to pH 6 at 40°C. 9,
p A g 8. The yield was adjusted to 0 and the yield was 100 g.

Potassium thiocyanate 3.0×10 −3 mol 1 mol Ag 1 sodium thiosulfate 3.0×IO−5 mol 1 mol Ag and potassium chloroaurate at 60°C]. 2×10-'mol 1 mol Ag was added, stirred for 40 minutes, chemically sensitized, and E
It was set as m-A. The obtained emulsion has an average equivalent circular diameter of 0.60μ
The particles were monodisperse octahedral particles with m and a coefficient of variation of circular radius of 9%.

(Production method of Em-B) In the production method of Em-A, (N
H4)2 PdCff144X10-' mol 1 mol Ag
Em-B
And so.

(Production method of Em-C) In the production method of Em-A, (NH4)2P d C l144X is added 10 minutes before adding the chemical sensitizer during chemical sensitization.
10-'mol 1 mol Ag and potassium thiocyanate 2X1
Em-C was prepared in the same manner as Em-A except that 0-3 mol 1 mol Ag was added.

(Production method of Em-D) Dissolve Em-A at 40°C, (NH4) Z P
d Add CE 44
The mixture was stirred for 30 minutes to obtain Em-D.

(Production method of Em-E) In the production method of Em-A, 2 minutes after the completion of the addition of the second stage silver nitrate aqueous solution, (NH4)2P d CHa 4XI
O-'mol 1 mol Ag and potassium thiocyanate 2X10
Em-E was prepared in the same manner as Em-A except that 1 mol Ag was added and stirred for 8 minutes, followed by desalting by flocculation method.

(Production method of Em-F) In the production method of Em-A, immediately before desalting by the flocculation method, (NH4)ZP d Cn44 Xl0-'
Ern-F was prepared in the same manner as Em-A except that 1 mol Ag and 2×10 −3 mol 1 mol Ag of potassium thiocyanate were added.

The emulsions Em-A to F and the protective layer were coated on a cellulose triacetate film support provided with an undercoat layer in the coating weights shown in Table 1.

Table 1 Emulsion coating conditions (1) Emulsion layer/emulsion... E m -A -F (Silver 2.1X10-2 mol/n) Coupler (1,5X10-3 mol/n?) Tricresyl Phosphate (1,10g/rrf)・Gelatin (2,30g/rff) (2) Protective layer・2,4-dichloro-6-hydroxy-5-)riazine sodium salt (0.08g/rff)・Gelatin (1.80 g/bo) These samples were left for 14 hours under the condition of 40'C1 relative temperature of 70%, and then exposed for 1/100 seconds through a continuous wedge to perform the next color development process.

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

Process Processing time Processing temperature Color development
2 minutes 00 seconds 40'C bleach fixing 3 minutes 00 seconds 40''C washing (1) 20
Seconds Wash with water at 35℃ (2) 20 seconds
Stable at 35°C for 20 seconds
Drying at 35°C 50 seconds 65
°C Next, the composition of the processing solution will be described.

(Color developer) (Unit g) Diethylenetriaminepentaacetic acid 2.01-Hydroxyethylidene-3,0 1,1-diphosphonic acid Sodium sulfite 4.0 Potassium carbonate Potassium bromide Potassium iodide Hydroxylamine sulfate 4-[N- Ethyl = N ~ β hydroxyethylamino] Add -2-methylaniline sulfate and H (bleach-fix solution) Ethylenediaminetetraacetic acid ferric ammonium trihydrate Ethylenediaminetetraacetic acid disodium salt Sodium sulfite ammonium thiosulfate aqueous solution (70%) Acetic acid (98%) 30.0 1.4 1,5 mg 2.4 4.5 1,OL 1,0.0 5 (unit g) 90.0 5.0 12.0 260.0mR 5,0m9゜Bleach accelerator 0.01 mo) 1 Add water 1・OLp) (
6,0 (Washing liquid) A mixed bed type in which tap water was filled with 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). Water was passed through the column to reduce the concentration of calcium and magnesium ions to 3 mg/L or less, and then 20 mg/L of sodium isocyanurate dichloride and 1.5 g/L of sodium sulfate were added.

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

(Stabilizing liquid) (Unit: g) /
[/'? Phosphorus (37%) 2.0 m
fl polyoxyethylene-p-0,3 monononylphenyl ether (average degree of polymerization 10) ethylenediaminetetraacetic acid 0.05 -Add sl.lium salt water 1. OLp H5
, 0-8,0 Sensitivity was expressed as a relative value of the reciprocal of the exposure amount expressed in lux seconds at a density of 0.2 on Capri.

The results are summarized in Table 2.

High sensitivity with low fog was achieved only by adding after the particle formation step of the present invention and before the desalting step. When a palladium compound is added during particle formation (Em-
B) No image was obtained.

Em-A and Em-E were each prepared in three replicates, each as E m A I + A z + A 3
and E m E I + E z + E 3,
The results shown in Table 3 were obtained by coating, exposing and developing in the same manner.

Table 3 Comparison of sensitivity/fogging between Em-A and Em-E It can be seen that the sensitivity/fog is extremely improved. In other words, the production of silver halide photographic emulsions is stabilized.

In the method for producing Em-C and Em-E, the time required for flocculation is changed to produce EmC and Em-E.
8 rounds of Em CI+C2 and Em
E4+E5 was coated, exposed and developed in the same manner as the fourth layer.
Obtained the results in the table.

As is clear from Table 3, by adding the palladium compound after the grain formation process of the present invention and before the desalting process, the repeatability of the emulsion is improved, as is clear from Table 4. It can be seen that the reproducibility of the emulsion is extremely good regardless of the time required for flocculation by adding it after the grain formation step of the present invention and before the desalting step. A stable manufacturing method was achieved.

Example-2 The dependence on the amount of palladium compound added will be explained.

(Production method of Em-G) Aqueous solution containing gelatin and KBr was maintained at 40°C, and a silver nitrate aqueous solution (A g N Oa, 32.
7g) and a halogen solution (KBr, 24.9g, Kl.

1.3 g) was added over 4 minutes. After adding an aqueous solution containing KBr and gelatin, the temperature was raised to 70°C, and then
An aqueous solution containing 6 cm of dimethylamine borane and an aqueous solution containing 100 mg of Compound 1-2 of Table A were added simultaneously. Then silver nitrate aqueous solution (AgNO3, 152, 3g)
Halogen aqueous solution (5.3% by weight of Kl based on KBr)
) was added over a period of 32.1 minutes. At this time, the silver potential of the reaction solution was maintained at OmV with respect to a saturated calomel electrode.

After that, silver nitrate aqueous solution (A g N○: +, 7.2 g)
and Na CI! , aqueous solution (NaCj2, 6.7g) at 1
．． It was added over a period of 5 minutes. Five minutes after the addition was completed, desalination was performed by flocculation method. Add gelatin, 40
The pH was adjusted to 6.9 and P A g to 8.0 at °C. This emulsion has an average thickness of 0.13 μm and an average equivalent circle diameter of 0.6
8 μm, coefficient of variation of circular phase diameter 28%, aspect ratio 5.
2 tabular grains.

To this emulsion, 1.40 x 10 (sensitizing dye A) mol 1 mol Ag of the following sensitizing dye was added, and then at 64°C, potassium thiocyanate 3.0 x 10 -3 mol 1 mol Ag, sodium thiosulfate Adding 4.8×10−′ mol 1 mol Ag, and 1.0×10−6 mol 1 mol Ag potassium chloroaurate;
Stir for 40 minutes and add 5XLO-' of anti-fog agent A below.
One mole of Ag was added and the temperature was lowered to obtain (antifoggant A) Em-G.

(Production method of Em-H) In the production method of Em-G, 30 seconds after the addition of silver nitrate, (NH4)Z P d Cj241 was added, stirred for 5 minutes, and then desalted using the flocculation method. Em-H was prepared in the same manner as Em-G.

(Production method of Em-1) In the production method of Em-G, 30 seconds after the addition of silver nitrate, (NH4)2PdcL 5X10-5 mol 1 mol Ag
and potassium thiocyanate 2.5 x 10-' mol 1 mol A
Em-G was prepared in the same manner as Em-G, except that after stirring for 5 minutes, the em-
■It was.

(Production method of Em-J) In the production method of Em-G, (NH4)2PdCj2.30 seconds after the addition of silver nitrate is completed. lXl0-' mol 1 mol Ag and potassium thiocyanate 5X10-' mol 1 mol A
Em-G was prepared in the same manner as Em-G, except that after stirring for 5 minutes, the em-
I made it J.

(Production method for Em-) In the production method for Em-G, 30 seconds after the addition of silver nitrate, (NH4)Z P d C1, a 4 X 10-'
Em- was prepared in the same manner as Em-G except that 1 mol Ag and potassium thiocyanate 2×10-' mol 1 mol Ag were added, stirred for 5 minutes, and then desalted by the flocculation method. .

(Production method of Em-L) In the production method of Em-I, 10 minutes before adding the chemical sensitizer during chemical sensitization, (NH4)2PdCn45X10-' 1 mole Ag and potassium thiocyanate 2.5X10-3
Em-L was prepared in the same manner as Em-■ except that 1 mol Ag was added.

E m -G -L with a coating aid and a hardening agent and 2g/n of Ag on the cellulose triacetate film base? It was applied so that The coating emulsion is a tungsten bulb (color temperature 2
854 K) for 1 second through a continuous wedge. The exposed coated emulsion was treated with the following surface developer (MAA).
-1) at 20°C for 10 minutes.

Metol 2.5g d-ascorbic acid 10.0g Potassium bromide
1.0g Navox 3
1000 mf with 5.0g water
The sensitivity of the obtained emulsion is that the optical density is fogged plus 0.1
It is expressed as a relative value of the reciprocal of the exposure amount required to achieve .

The results obtained are shown in Table 5.

Table 5 Comparison of Em-GL Sensitivity/Full As is clear from Table 3, palladium compound was added at 5X10-
By adding 5 mol or more, high sensitivity was achieved with low fog.

Example 3 The effect of the emulsion of the present invention in a multilayer color light-sensitive material will be explained.

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 the amount expressed in g/nK of silver for silver halide and colloidal silver, and the amount expressed in g/rrY for coupler additives and gelatin.
In addition, the number of moles of the aggravating 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.

U■: Ultraviolet absorber, 5olvH high boiling point organic solvent, Ex
F: Dye, ExS: Enhanced dye, ExC: Cyan coupler, ExM: Magenta coupler ExY: Yellow coupler, Cpd: Additive 1st layer (antihalation layer) Black colloidal silver 0.15 Gelatin 2.9U V -1
0,03 UV -20,06 UV -30,07 Sol v-20,08 Ex F-10,01 EχF -20,01 2nd layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide Emulsion (AgI 4 mol%, average-AgI type, equivalent circle diameter 0.6 μm, thickness 0.2 μm, coefficient of variation of equivalent circle diameter 37%, tabular grains, diameter/thickness ratio 3.0) Coated silver amount 0.4 Gelatin 0.8E x
S -16,9X10-' ExS-25,2X10 ' Ex S-56,9X10-' Ex C-72,4X10-5 Ex C-10,17 Ex C-20,03 Ex C-30,13 Third layer (medium-sensitivity red-sensitivity emulsion layer) Silver iodobromide emulsion (AgI 6 mol%, core-shell ratio 2:
1 internal high Agl type, equivalent sphere diameter 0.65 μm, coefficient of variation of equivalent sphere diameter 25%, plate-like grains, diameter/thickness ratio 2.0) Coated silver amount 0.65 Silver iodobromide emulsion (Agr 4 mol%) , uniform AgI type, equivalent sphere diameter 0.4 μm, coefficient of variation of equivalent sphere diameter 37%, plate-like particles,
Diameter/thickness ratio 2.0) Coated silver amount 0.1 Gelatin 1.0ExS
-12X10-' Ex S-21,2X10-'ExS-52X10-' ExS-77X10-6 Ex C-10,31 ExC-20,01 Ex C-30,06 Fourth layer (high sensitivity Emulsion layer) Silver iodobromide emulsion (AgI 6 mol%, core shell ratio 2:
1 inner cylinder Agl type, equivalent sphere diameter 0.7 μm, coefficient of variation of equivalent sphere diameter 25%, plate-shaped particles, diameter/thickness ratio 2.5) Coated silver amount 0.9 Gelatin 0.8B x
S -11,6X10-' Ex S -21,6X10-' Ex S -51,6X10-'BxS-76X10-' ExC-10,07 ExC-40,05 Solv-10,07 S o I v- 20,20 Cp d -74,6X10-' 5th layer (middle layer) Gelatin 0.6U V
-40,03 UV-50,04 Cp d-10,1 Polyethyl acrylate latex 0.08So
lv-10,05 6th layer (low-sensitivity green-sensitive milk side layer) Silver iodobromide emulsion (AgI 4 mol%, uniform Ag1 type, equivalent sphere diameter 0.4 μm, coefficient of variation of equivalent sphere diameter 37%, plate shaped particles, diameter/thickness ratio 2.0) Coated silver amount 0.18 Gelatin 0.4ExS
-32X10-'ExS-47X10-'ExS-51XIO-' ExM-50,11 EχM-70,03 E x Y -80,01 Solv-10,09 S o I v-40,01 7th layer (medium sensitivity Green-sensitive emulsion layer) Odor (1 [emulsion (AgI 4 mol%, core shell ratio 1:1
Surface height AgI type, circular bubble diameter 1.0μm, thickness 0.2μm
m, coefficient of variation of circle equivalent diameter 15%, tabular grain, diameter/thickness ratio 5.0) Coated silver amount 0.27 Gelatin 0.6ExS
-34X10-' Ex S-41, 4X10-3 ExS-52 High-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (Agr 8.7 mol%, multilayer structure grains with silver content of 3 = 4:2 from the inside, Agl content of 2 from the inside)
4 mol, 0 mol, 3 mol%, equivalent sphere diameter 0.7 μm, coefficient of variation of equivalent sphere diameter 25%, plate-shaped particles, diameter/thickness ratio 1.6
) Coated silver amount 0.7 Gelatin 0.8E x
S -45,2X10-' Ex S-51Xl0-' Ex M-50, I ExM-60,03 ExY-80,02 Ex C-10,02 EχC-40,01 Solv-10,25 S o I v-20,06 Solv-40,01 Cpd-71XIO-' 9th layer (middle layer) Gelatin 0.6Cp d
-10,04 Polyethyl acrylate latex 0.12So
lv-10,02 10th layer (donor layer for interlayer effect on red-sensitive layer) Silver iodobromide emulsion (Ag1 6 mol%, internal high AgI type with core-shell ratio 2:1, equivalent sphere diameter 0.7 μm, equivalent to sphere) Coefficient of variation in diameter 25%, plate-like grains, diameter/thickness ratio 2.0) Coated silver amount 0.68 Silver iodobromide emulsion (Ag1 4 mol%, uniform Agl type, equivalent sphere diameter 0.4 μm, equivalent sphere Coefficient of variation in diameter 37%, plate-like particles, diameter/thickness ratio 2.5 Coated silver amount Gelatin xt-36 xM-10 0Iv-1 11th layer (yellow filter layer) Yellow colloidal silver gelatin Pd-2 olv-1 pd -1 pd-6 12th layer (low sensitivity blue-sensitive emulsion layer) E m -G -L Coated silver amount Gelatin xC-1 xC-4 0.19 1.0 XIO-' 0.19 0.20 0.06 0.8 0.13 0.13 0.07 0.002 0.13 0.45 1.8 0.06 0, O3 ExY-90,14 ExY-110,89 Solv-10,42 13th layer (intermediate layer) Gelatin 0.7ExY-
120,20 Solv-10,34 14th layer (high sensitivity blue-sensitive emulsion layer) Silver chloroiodobromide emulsion (Agl B mol%, internal high AgT type, Ag (47 mol%, inner shell AgCβ type, circle equivalent diameter 2.0
μm, thickness 0.3 μm, coefficient of variation of circle equivalent diameter 30%, tabular grain, diameter/thickness ratio 7.0) Coated silver amount 0.5 Gelatin 0.5ExS-
67X10-' Ex Y-90,01 ExY-110,20 Ex C-10,02 Solv-10,10 15th layer (first protective layer) Fine grain silver iodobromide emulsion (Ag1 2 mol%, uniform Agl type, equivalent sphere diameter 0.07μm) Coated silver amount 0.12 Gelatin 0.9U V
-40,11 UV-50,16 S o I v-50,02 H-10,13 0pd-50,10 Polyethyl acrylate Latinx 0.09 1st
6th layer (second protective layer) Fine grain silver iodobromide emulsion (AgI 2 mol%, homogeneous -Agl
Mold, equivalent sphere diameter 0.07 μm) Coated silver amount 0.36 Gelatin 0.55 Polymethyl methacrylate particles (diameter 1.5 μm) 0.2H
-10,17 In addition to the above components, each layer contains an emulsion stabilizer cp d-
3 (0,07 g/rrT), surfactant Cpd4 (0
, 03 g/m) was added as a coating aid.

In addition, SP (,
-1,5PC-2 was added. The structural formulas of the compounds used are shown in Table 8.

Em-G, HT prepared in Example-2 in the 12th layer,
The samples using J, K, and L were respectively designated as sample 301.
302, 303, 304, 305 and 306.

After exposing the color photographic materials 301 to 306 as described above, they were processed using an automatic processor in the manner described below (until the cumulative amount of bleaching solution replenished was three times the volume of the mother liquor tank).

Process color development bleached white Water washing fixed arrival place processing time 3 minutes 15 seconds 6 minutes 30 seconds 2 minutes 10 seconds 4 minutes 20 seconds Washing with water (2) 1 minute 00 seconds Stability 1 minute 05 seconds Drying 4 minutes 20 seconds Refill amount is 35mm width 1 method Processing temperature Replenishment amount 38°C 15m 12° 38°C10m I2° 35°C10mff 38°C 20m E 35°C 20m j2 38°C10mj2 55°C per m length tank capacity 20I.

0L 0L 0L 0L 10■5 Next, the composition of the treatment liquid will be described.

(Color developer) Diethylenetriaminepentaacetic acid 1-hydroxyethylidene 1.1-diphosphonic acid Sodium sulfite mother solution (turbidity) Replenisher (g) 1.0 1.1 3.0 3.2 4.0 4.9 Potassium carbonate bromide Potassium iodide Potassium hydroxylamine sulfur M salt 4-(N-ethyl-N-β hydroxyethylamino) Add 2-methylaniline sulfate to pH (bleach solution) Ethylenediaminetetraacetic acid Sodium ferric trihydrate Ethylenediaminetetraacetic acid Disodium salt ammonium bromide ammonium nitrate aqueous ammonia (27%) Add water to pH 30,0 1,4 1,5mg 2.4 4.5 1.0L 10.05 30.0 3.6 7.2 ■, 0L 10.10 Mother liquor (turbidity) Replenishment solution (turbidity 100.0 140.0 10.0 140.0 30.0 6.5m 1, OL 6.0 11.0 180.0 40.0 2.5m1 1, OL 5.5 (Fixer) Mother liquor (g) Replenisher (g) Ethylenediaminetetraacetic acid 0.5 1.0 Disodium salt Sodium sulfite 7.0 12.0 Sodium bisulfite 5.0 9.5 Ammonium thiosulfate 170.0ml 240.
0ml aqueous solution (70%) Add water L, OL 1.0
LPH6, 76, 6 (Water solution) Mother liquor and replenisher Common tap water was mixed with an H-type strongly acidic cation exchange resin (Amberly 1iR-120B manufactured by Rohm and Haas) and an OH-type anion exchange resin (Amberly IR-400 manufactured by Rohm and Haas). ) was passed through a mixed bed column packed with water to reduce the concentration of calcium and magnesium ions to 3 mg/L or less, and then 20 mg/L of sodium isocyanurate dichloride and 1.5 g/L of sodium sulfate were added.

The pH of this solution was in the range of 6.5-7.5.

(Stable solution) Table 6 Comparison of sensitivity of samples 301 to 306 mother liquor (g)
Replenisher ((2) Formalin (37%) 2.0ml 3
．． 0ml polyoxyethylene-p-0,30,45 monononyl phenyl ether (average degree of polymerization 10) ethylenediaminetetraacetic acid 0.05 0.08
Add sodium salt water 1. OL 1.0
LpH5,0-8,05,0-8,0 1.0 from Kafuri concentration regarding the characteristic curve of dark color image
Sensitivity is expressed as a relative value of the reciprocal of the exposure amount that gives a high density.

The results obtained are shown in Table 6.

As is clear from Table 6, high sensitivity was achieved by adding a palladium compound of 5×10 −5 mol or more per mol of silver halide after the grain formation step and before the desalting step.

(Effects of the Invention) According to the present invention, a stable method for producing a silver halide photographic emulsion can be achieved. In particular, a method for producing a silver halide photographic emulsion that is reduction sensitized in the grain forming step can be achieved.

Table A CH35OzSNa CzH5S02SNa C3H7SO□5K C4H9SO□5Li C6H+3sOzsNa C8H,7SO2SNa CH3(CH2)3CHCH2SO□S, Nll.

C2I+5 C,oHz+5OzsNa (:, J25SO2SNa C+6H33SOzSNa CHz-CHCHzSOzSNa t-C4H9SO□5Na C)130cHzcHzsO□5-NaC2H5SO□
S H3 CaHI7SO2SC1l□CH3 C2H5SO□5CH2C]I2CN KSSO7(CJlz)zso□5K NaSSOz (Ctlz) n5OzsNaNaSS
Oz (CHz) aS (CI+2) n5OzsN
a) CztlsSOzSCHzCHzSOzCHzCHzS
SO□C2)1. .

CH3SSO7(C11□)4SO2SCIl:1CH
3SSO7(CH2)2SO□5C113C2H,,S
o□5CHzN CHzCthNCH2SSO□C2
H5 CH2C1(.OHCHzCII□0HC2H5SO□
5sso□C2H,.

(n) C3117SO2SSSOZC3H7 (n)th B table olv o1 trihexyl phosphate xF V H3 H3 V olv ■ tricresyl phosphate olv dibdel phthalate xS xS xS xS xS xS xS xC H I xC 0■ xM H3 EχC H EχC H xM A record xM CI! .

xM xY xY xY pd pd pd ■ pd pd CH3 PC ■ PC -(-CH CH2 → bottom COOC2H5

Claims (2)

[Claims] (1) A method for producing a silver halide photographic emulsion, which comprises adding at least 5 x 10^-^5 moles of palladium compound per mole of silver halide after the grain formation step and before the desalting step. (2) The method for producing a silver halide photographic emulsion according to claim (1), wherein the silver halide grains are reduction sensitized in the grain forming step.