JP2514707B2 - Method for producing silver halide photographic emulsion - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Use) The present invention relates to a method for producing a silver halide photographic emulsion. More specifically, it relates to a stable method for producing a silver halide photographic emulsion having high sensitivity and low fog. In particular, the present invention relates to a stable method for producing a silver halide photographic emulsion which has been reduction-sensitized in the grain forming step.

(Prior Art) U.S. Pat. No. 2,448,060 discloses that sensitivity is increased by adding a palladium compound and ascorbic acid after sulfur sensitization of an emulsion and before coating.
U.S. Pat. No. 2,598,079 discloses that a low illuminance sensitivity is particularly enhanced by adding a palladium compound after gold / sulfur sensitization of an emulsion and before coating.
U.S. Pat.Nos. 2,472,627, 2,472,631, 2,566,245 and 2,566,263 disclose that the storage stability of a sensitive material under high temperature and high humidity is improved by adding a palladium compound after chemical sensitization of an emulsion. Is disclosed.

British Patent No. 1,351,309 states that a noble metal salt is added to the silver halide during the silver halide grain formation process (at the time of conversion).
It is disclosed to add 3 × 10 ^{−7 to} 3 × 10 ⁻⁵ mol per mol.

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

In JP-A-61-67845, monodisperse core / shell type silver halide grains having different silver iodide contents in the vicinity of the surface and in the inside are used as chalcogen sensitizers, gold sensitizers and water-soluble salts of palladium. Of silver halide emulsions which are chemically ripened in the presence of at least one of JP 62-2126
No. 41, a silver halide emulsion for chemically sensitizing silver halide grains having a (nn1) face in the presence of at least one of a chalcogen sensitizer, a gold sensitizer and a compound of a noble metal of Group VIII of the periodic table. Is disclosed.

On the other hand, JP-A-48-87825 discloses that the addition of a reducing agent in the step of forming grains of silver halide increases the sensitivity with a decrease in gradation. In Japanese Examined Patent Publication No. 58-1410, gradation is lowered by adding a reducing agent in the silver halide grain formation step and further adding an oxidizing agent until the final size of the silver halide is reached. It is disclosed that the sensitivity is increased without being accompanied by. The effect of the present invention is particularly remarkable when the present invention is applied to the above emulsion in which the reducing agent and the 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 halide photographic emulsion having high sensitivity and less fog.

Another object of the present invention is to provide a stable production method of the above silver halide photographic emulsion. In particular, it is to provide a stable method for producing a silver halide photographic emulsion which has been subjected to reduction sensitization during the grain formation process.

(Means for Solving the Problems) The above-mentioned object of the present invention can be achieved by the oyster means. That is, in the method for producing a silver halide photographic emulsion comprising the steps of grain formation, desalting and chemical sensitization, after the grain formation step of the silver halide grains which have been reduction sensitized in the grain formation step, the desalting step This can be achieved by a method for producing a silver halide photographic emulsion, which is characterized by adding 5 × 10 ⁻⁵ mol or more of a palladium compound per mol of silver halide.

 Hereinafter, the present invention will be described in detail.

The steps for producing a silver halide emulsion are roughly classified into steps such as grain formation, desalting, chemical sensitization and coating. Particle formation is subdivided into nucleation, ripening, growth and the like. These steps are not performed uniformly, but chemical sensitization is performed simultaneously with grain formation, or chemical sensitization is repeated.
The addition of the palladium compound after the grain forming step and before the desalting step means that the palladium compound is added after the addition of the silver salt solution in grain formation and before the desalting step. That is, it may be at the same time as the end of the addition of the silver salt solution, or at any time between the end of the addition of the silver salt solution and the desalting step. The palladium compound may be added all at once, divided into several parts, or continuously added for a predetermined period of time. It may be aged after the addition of the palladium compound and before the desalting step, or may be left at high temperature for a long time after the addition of the palladium compound and before the desalting step.

The palladium compound in the present invention is added in an amount of 5 × 10 ^-5 mol or more per mol of silver halide. Preferably 1 × 10 ^-3
Add not more than mol. Most preferably, the palladium compound is added in an amount of 1 × 10 ^-4 mol to 5 × 10 ^-4 mol per mol of silver halide. If it is 1 × 10 ^-5 mol or less, the effect of the present invention cannot be obtained, and conversely, if it is 1 × 10 ^-3 mol or more, other adverse effects occur.

Here, the palladium compound means a divalent salt or a tetravalent salt of palladium. Preferably the palladium compound is R ₂
Expressed as PdX ₆ or R ₂ PdX ₄ . Where R is a hydrogen atom,
Represents an alkali metal atom or an ammonium group. X represents a halogen atom and represents a chlorine, bromine or iodine atom. Specifically, K ₂ PdCl ₄ , (NH ₄ ) ₂ PdCl ₆ , Na ₂ PdCl ₄ or (NH ₄ ) ₂ PdCl ₄ is preferable. PdCl ₂ ,, PdCl ₂・ 2H ₂ O, Pd (N
H ₃ ) ₄ Cl ₂ , (NH ₃ ) ₂ PdCl ₂ , PdI ₂ , Pd (OH) ₂ , Pd (SO ₄ ), Pd
(NO ₃ ) ₂ , Na ₂ Pd (NO ₃ ) ₄ or (NH ₃ ) ₂ PdCl ₄ may be used, but a water-soluble palladium compound is preferable. Most preferably, these palladium compounds are used in combination with a thiocyanate ion at least 5 times the molar amount of the palladium compound.

The addition conditions of the palladium compound are arbitrary. That is, the temperature may be 30 ° C. or more and 80 ° C. or less. Preferably 40 ° C or higher,
It is below 70 ℃. Arbitrary values are allowed for pH and pAg.
Preferably, the pH is between 4 and 10.

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

The fact that reduction sensitization is applied to the grain forming step of the silver halide emulsion basically means that it is performed during nucleation, ripening and growth. The reduction sensitization may be carried out at any stage of nucleation, physical ripening and growth which are the initial stages of grain formation. Most preferred is a method of reduction sensitization during growth of silver halide grains. The term "during growth" here also refers to a method in which the silver halide grains are physically ripened or subjected to reduction sensitization while they are growing by the addition of a water-soluble silver salt and a water-soluble alkali halide, and the growth is temporarily stopped during the growth. It means that the method also includes a method of performing reduction sensitization in the above state and then further growing.

The reduction sensitization of the present invention refers to a method in which a known reducing agent is added to a silver halide emulsion, and a low pAg of pAg1 to 7, which is called silver ripening.
Method of growing or aging in high temperature atmosphere, high pH
Any method of growing or aging in a high pH atmosphere of pH 8 to 11, which is called aging, can be selected. Also, two or more methods can be used in combination.

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

As reduction sensitizers, first silver salts, amines and polyamines, hydrazine derivatives, formamidine sulphonic acid,
Silane compounds, borane compounds and the like are known. The present invention can be used by selecting from these known compounds,
Two or more compounds can be used in combination. Preferred compounds as the reduction sensitizer are silver chloride, thiourea dioxide and dimethylamine borane. Since the addition amount of the reduction sensitizer depends on the emulsion production conditions, it is necessary to select the addition amount, but an appropriate range is from 10 ^-8 to 10 ^-3 mol per mol of silver halide.

The reduction sensitizer can be dissolved in water or a solvent such as alcohols, glycols, ketones, esters and amides and added during grain formation. It may be added to the reaction vessel in advance, but it is preferable to add it at an appropriate time for 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 grains may be formed using these aqueous solutions. In addition, it is also a preferable method to add the solution of the reduction sensitizer in several batches or to add the solution continuously as the grains are formed.

More preferably, at least one compound selected from the compounds represented by the following general formulas [I], [II] and [III] is allowed to coexist in the production process of the reduced and published special silver halide emulsion.

[I]

RSO in ₂ S-M (II) RSO ₂ S-R ¹ (III) _{RSO 2 S-Lm-SSO 2} -R 2 Formula, R, R ^1, R ² 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, and m is 0 or 1.

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

The compounds of the general formulas [I], [II] and [III] will be described in more detail. When R, R ¹ and R ² are aliphatic groups, saturated or unsaturated, straight chain, branched or cyclic, An aliphatic hydrocarbon group, preferably an alkyl group having 1 to 22 carbon atoms,
An alkenyl group and an alkynyl group each having 2 to 22 carbon atoms, which may have a substituent. Examples of the alkyl group include methyl, ethyl, propyl, butyl,
Pentyl, hexyl, octyl, 2-ethylhexyl,
Examples include decyl, dodecyl, hexadecyl, octadecyl, sillohexyl, isopyropyr and t-butyl.

Examples of the alkenyl group include allyl and butenyl.

Examples of the alkynyl group include a propargyl group and butynyl.

The aromatic group of R, R ¹ and R ² includes a monocyclic or condensed ring aromatic group, preferably having 6 to 20 carbon atoms, and examples thereof include phenyl and naphthyl. These may be substituted.

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

Substituents for R, R ¹ and R ² include, for example, alkyl groups (eg, methyl, ethyl, hexyl), alkoxy groups (eg, methoxy, ethoxy, octyl), aryl groups (eg, phenyl, naphthyl, tolyl), hydroxy. Base,
Halogen atom (fluorine, chlorine, bromine, iodine), aryloxy group (eg, phenoxy), alkylthio group (eg, methylthio, butylthio), arylthio group (eg, phenylthio), acyl group (eg, acetyl, propionyl, butyryl, valeryl) ), A sulfonyl group (eg, methylsulfonyl, phenylsulfonyl), an acylamino group (eg, acetylamino, benzoylamino), a sulfonylamino group (eg, methanesulfonylamino, benzenesulfonylamino), an acyloxy group (eg, acetoxy, benzoxy). , Carboxyl group, cyano group, sulfo group, amino group, -SO ₂ SM group, -SO ₂
Examples include R ¹ groups.

The divalent linking group represented by L 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, an arylene group, -O-, -S-, -NH-,
-CO -, - SO ₂ - is made of a single or combination of such.

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

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

M is preferably a metal ion or an organic cation. Examples of the metal ion include lithium ion, sodium ion, and potassium ion. Examples of the organic cation include ammonium ion (eg, ammonium, tetramethylammonium, tetrabutylammonium), hostnium ion (eg, tetraphenylphosphonium), and guanidyl group.

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

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

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

The compound of the general formula [I], [II] or [III] is disclosed in JP-A-54-1019; British Patent 972,211: Journal of Organic Chem.
It can be easily synthesized by the method described or cited in istry (Journal of Organic Chemistry) 53, 396 (1988) and Chemical Abstracts (Chemical Abstracts) 59, 9766e.

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

The compound represented by the general formula [I], [II] or [III] can be added during the production process of the silver halide emulsion.
The method usually used when adding an additive to a photographic emulsion can be applied. For example, a water-soluble compound is prepared as an aqueous solution having a suitable concentration, and a water-insoluble or sparingly-soluble compound is a suitable organic solvent miscible with water, such as alcohols, glycols, ketones, esters, amides. So, dissolve in a solvent that does not adversely affect photographic characteristics,
Can be added.

The compound represented by the compound [I], [II] or [III] may be added at any stage during grain formation of the silver halide emulsion, before or after chemical sensitization and during production. Preferred is a method of adding the compound before or during the reduction sensitization. In the present invention, it is preferable that the thiosulfonic acid-based compound is allowed to exist during the silver halide grain formation step to carry out reduction sensitization.

The thiosulfonic acid compound of the present invention may be added to the reaction vessel in advance, but it is preferable to add it at an appropriate time for particle formation. Further, the compounds [I] to [III] may be added in advance to an aqueous solution of a water-soluble silver salt or a water-soluble silver halide alkali, and grains may be formed using these aqueous solutions. In addition, it is also a preferable method to add the solutions of the compounds [I] to [III] in several times with the formation of particles or to continuously add them for a long time.

The most preferred compound in the present invention is a compound represented by the general formula [I].

In the photographic emulsion used in the present invention, any silver halide such as silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used. Preferred silver halides are silver iodobromide, silver chloroiodobromide, silver bromide and silver chlorobromide containing 30 mol% or less of silver iodide.

The silver halide grains that can be used in the silver halide emulsion of the present invention include regular crystals that do not include twin planes (regular),
Particles containing twin planes as described in the Photographic Society of Japan, Photographic Industry Basic Silver Halide Photography (P.163), for example, single twin containing one twin plane, parallel twin It can be selected from parallel multiple twins including two or more crystal planes and non-parallel multiple twins including two or more non-parallel twin planes according to the purpose. In the case of normal crystals, a cube consisting of (100) faces, an octahedron consisting of (111) faces, JP-B-55-42737,
1 composed of (110) plane disclosed in JP-A-60-222842
Dihedral grains can be used. Further Journal of Im
aging Science, Vol. 30, p. 247 (h11) plane particles typified by (211), (hh1) plane particles typified by (331), and (210) plane typified (hk).
The (hk1) plane particles typified by the (0) plane particles and the (321) plane can also be selected and used according to the purpose for which the preparation method needs to be devised. (100) and (111) faces coexist in one particle 14
Depending on the purpose, particles that have two or a large number of surfaces, such as a surface grain, a particle in which the (100) surface and the (110) surface coexist, or a particle in which the (111) surface and the (110) surface coexist, are selected according to the purpose. Can be used.

The grain size of these silver halide grains may be fine grains of 0.01 micron or less or large size grains having a projected area diameter of up to 10 microns, and may be a monodisperse emulsion having a narrow distribution or a polydisperse emulsion having a wide distribution. But yes.

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

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Grafkid, published by Paul Montell (P. Glafkides, Ch.
imie et Physique Photographique Paul Montel, 196
7), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (GFDuffin, Photographic Emulsion Chemistry
(Focal Press, 1966), "Manufacturing and coating of photographic emulsions" by Zelikmann et al., Published by Focal Press (VLZelikman et.
al, Making and Coating Photographic Emulsion, Focal
Press, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method, or the like may be used, and as a method of reacting a soluble silver salt and a soluble halogen salt, a one-sided mixing method, a simultaneous mixing method,
Any combination of them may be used. A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one form of the simultaneous mixing method, a method of keeping pAg in a liquid phase where silver halide is formed constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

The silver halide emulsion comprising the regular grains,
Obtained by controlling pAg and pH during particle formation.
For more information, see, for example, Photographic Science and Eng
ineering, Vol. 6, pp. 159-165 (1962);
Journal of Pho
tographic Science), 12, 242-251 (1964), U.S. Pat. No. 3,655,394 and British Patent 1,413,748.

Further, tabular grains having an aspect ratio of 3 or more can be used in the present invention. Tabular grains are described in Cleve, Photography Theory and Pra
ctice (1930), p. 131; Gatov, Photographic Science and Engineering (Gutoff, Pho
tographic Science and Engineering), Volume 14, 248-
257 (1970); U.S. Pat. Nos. 4,434,226 and 4,414,31
No. 0, 4,433,048, 4,439,520 and British Patent No.
It can be easily prepared by the method described in 2,112,157 and the like. The use of tabular grains has advantages such as an increase in covering power and an increase in color sensitization efficiency by a sensitizing dye, which is described in detail in US Pat. No. 4,434,226 cited above.

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

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

The silver halide emulsion of the present invention preferably has a distribution or structure with respect to the halogen composition in its grains. Typical examples are JP-B-43-13162 and JP-A-61-2.
15540, JP-A-60-222845, JP-A-61-75337, and the like, which are core-shell type or double-type type grains having a halogen composition in which the inside and the surface layer of the grains are different. In such particles, the shape of the core part and the entire shape with the shell may be the same or different. Specifically, the core has a cubic shape,
The shape of the shelled particles may be cubic or octahedral. On the contrary, the core part may be an octahedron and the particles with shell may have a cubic or octahedral shape. In addition, although the core portion is a regular regular particle, the particle with shell may be slightly deformed or have an irregular shape. Further, it is not a simple double structure, but is disclosed in JP-A-60-222844.
It is possible to form a triple structure as disclosed in US Pat.

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

In the case of a junction structure, it is naturally possible to combine silver halides with each other, but a silver salt compound not having a rock salt structure, such as silver rhodan or silver carbonate, can be combined with silver halide to form a junction structure. In addition, a non-silver salt compound such as PbO may be used as long as a junction 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 portion has a high silver iodide content and the shell portion has a low silver iodide content, conversely, The grains may have a low silver halide content and a high shul part. Similarly, with respect to the grains having a junction structure, the grains having a high silver iodide content in the host crystal and a relatively low silver iodide content in the junction crystal may be used, or vice versa.

Further, the boundary portion where the halogen composition of the grains having these structures is different may be a clear boundary or an unclear boundary by forming a mixed crystal due to a composition difference, and also a positive structural change. You can use the one with.

The silver halide emulsion used in the present invention is EP-0096727B1, EP.
-1164412B1 and other treatments for rounding particles, or DE-2306447C2, JP-A-60-221
Surface modifications may be performed as disclosed in 320.

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

Silver halide solvents are useful in promoting ripening.
For example, it is known to have excess halogen ions present in the reactor to accelerate aging. Therefore, it is clear that mere introduction of a halide salt solution into the reactor can accelerate aging. Other ripening agents can be used, and the total amount of these ripening agents can be added to the dispersion medium in the reactor before the addition of silver and halide salts, or 1 or 2 or more. It is also possible to add the halide salt, silver salt or peptizer of the above and to introduce them into the reactor. As another variant, the ripening agent can 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 emulsion is after the grain formation step (after precipitation formation or physical ripening), and after addition of the palladium compound, the soluble salts are removed (desalting step), which has long been known as a means. A Nudel water washing method in which gelatin is gelled may be used, and inorganic salts composed of polyvalent anions such as sodium sulfate, anionic surfactants, anionic polymers (eg polystyrene sulfonic acid), or gelatin derivatives (eg A precipitation method (flocculation) using an aliphatic acylated gelatin, an aromatic acylated gelatin, an aromatic carbamoylated gelatin, etc. may be used.

The emulsion produced by the production method of the present invention is chemically sensitized even after the desalting step. It is preferably 45 ° C or higher, more preferably 50
Chemically sensitizes above ℃. Chemical sensitization is preferably performed for 5 minutes or more, more preferably 10 minutes or more. In this chemical sensitization, active gelatin and compounds containing sulfur capable of reacting with silver (for example, thiosulfates, thioureas, mercapto compounds,
Sulfur sensitization method using rhodanines); selenium sensitization method; reducing substances (eg, primary tin salts, amines, hydrazine derivatives, formamidinesulfinic acid, silane compounds)
Reduction sensitization method using; noble metal compounds (gold complex salts, P
A noble metal sensitization method using a complex salt of t, Ir) or the like can be used alone or in combination. Of these, chemical sensitization by the sulfur sensitization method, the selenium sensitization method, or the gold complex salt sensitization method is preferably used alone or in combination.

The most preferable 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. It is preferably carried out at pH 5 or higher. Most preferably pH 6 or higher
6.5 or higher is effective for the present invention. The upper limit is 9 or less. It is preferably 8.5 or less.

Chemical sensitization is usually performed with pAg of 10 or less and 6 or more. It is preferably 9 or less and 7 or more.

The photographic emulsion of the present invention and used in the present invention contains various compounds for the purpose of preventing fog during the production process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. You can That is, azoles, for example, benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiazoles,
Aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole) and the like;
Mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadrinethione; azaindenes, such as triazaidenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetraazaindenes), Many compounds known as antifoggants or stabilizers, such as pentaazaindenes, can be added. For example, U.S. Patent 3,954,474
Nos. 3,982,947, and Japanese Patent Publication No. 52-28,660 can be used.

The photographic emulsion used in the present invention may be spectrally sensitized with methine dyes or the like. The dyes used include
Cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes are included. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei normally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiozoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus and the like; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these Nuclei of aromatic hydrocarbon rings fused to the nuclei of indolenin, benzindolenine nuclei, indole nuclei, benzoxadol nuclei, naphthoxazole nuclei, benzothiazole nuclei, naphthothiazole nuclei, benzoselenazole nuclei, benz Imidazole nucleus, quinoline nucleus, etc. can be applied. These nuclei may be substituted on carbon atoms.

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

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

In addition to the sensitizing dye, a dye having no self-spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion.

The dye may be added to the emulsion at any stage of emulsion preparation known to be useful so far. Most commonly, it is performed after the completion of chemical sensitization and before coating, but as described in U.S. Pat.Nos. 3,628,969 and 4,225,666, spectral sensitization is performed at the same time as chemical sensitization. Can be performed simultaneously with chemical sensitization,
It can be carried out prior to the chemical sensitization as described in JP-A-58-113,928, or the spectral sensitization can be started by adding silver halide grain precipitate formation before completion. It is also possible to add these said compounds separately, as taught in U.S. Pat.No. 4,225,666, i.e. to add some of these compounds prior to chemical sensitization and the balance after chemical sensitization. Additions are also possible and can be at any time during silver halide grain formation, including the method taught in US Pat. No. 4,183,756.

The addition amount is 4 × 10 ⁻⁶ to 1 × per mol of silver halide.
Although it can be used in an amount of 10 ^-2 mol, about 5 x 10 ^{-5 to} 6 x 10 ^-3 mol is more effective when the silver halide grain size is 0.2 to 1.2 µm.

The above-mentioned various additives are used in the light-sensitive material of the present technology, but various additives other than the above can be used depending on the purpose.

These additives are described in more detail in Research Disclosure I tem 17643 (December 1978) and I tem 1
8716 (November, 1979), the relevant parts are summarized in the table below.

Various color couplers may be used in the photographic material of the present invention, specific examples of which are described in the patents described in Research Disclosure (RD) No. 17643, VII-CG. .

As the yellow coupler, for example, U.S. Pat.
No. 501, No. 4,022,620, No. 4,326,024, No. 4,40
1,752, Japanese Patent Publication No. 58-10739, British Patent No. 1,425,020
And No. 1,476,760 are preferable.

As the magenta coupler, 5-pyrazolone-based and pyrazoloazole-based compounds are preferable.
4,310,619, 4,351,897, European Patent No. 73,636,
U.S. Pat.Nos. 3,061,432, 3,725,067, Research
Disclosure No. 24220 (June 1984), JP 60
-33552, Research Disclosure No. 24230 (1
June 984), JP-A-60-43659, U.S. Pat. No. 4,500,63.
Nos. 0 and 4,540,654 are particularly preferred.

Cyan couplers include phenol-based and naphthol-based couplers, for example, U.S. Pat. No. 4,052,212.
Issue No. 4,146,396, No. 4,228,233, No. 4,296,20
No. 0, No. 2,369,929, No. 2,801,171, No. 2,772,1
No. 62, No. 2,895,826, No. 3,772,002, No. 3,758,
No. 308, No. 4,334,011, No. 4,327,173, West German Patent Publication No. 3,329,729, European Patent 121,365A, U.S. Patent No. 3,446,622, No. 4,333,999, No. 4,451,559,
Those described in the above-mentioned 4,427,767 and European Patent 161,626A are preferable.

For example, Research Disclosure No. 17643 is a colored coupler for correcting unnecessary absorption of a coloring dye.
VII-G, U.S. Pat. No. 4,163,670, Japanese Examined Patent Publication No. 57-3941.
Those described in U.S. Pat. No. 3,004,929, U.S. Pat. No. 4,004,929 and U.S. Pat. No. 4,146,368 are preferred.

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

Typical examples of polymerized dye-forming couplers are U.S. Pat.Nos. 3,451,820, 4,080,211 and 4,367,282.
No. 2,102,173 and the like.

Couplers that release a photographically useful residue upon coupling can also be preferably used in the present invention. DIR couplers that release development inhibitors are RD17643, VII-F described above.
Patents described in paragraphs, JP-A-57-151944 and JP-A-57-1542
The compounds described in U.S. Pat. No. 34,60-184248 and U.S. Pat. No. 4,248,962 are preferable.

As a coupler that releases a nucleating agent or a development accelerator in an image state during development, for example, British Patent No. 2,097,140,
JP-A-2,131,188, JP-A-59-157638, JP-A-59-170840
Those described in the above item are preferred.

Other couplers that can be used in the light-sensitive material of the present invention include, for example, competitive couplers described in U.S. Pat.No. 4,130,427, U.S. Pat.Nos. 4,283,472, and 4,338,3.
No. 93, No. 4,310,618 and the like, multi-equivalent couplers, DIR redox compounds or DIR coupler releasing couplers described in JP-A-60-185950, JP-A-62-24252 and the like, and European Patent 173,302A. Couplers that release dyes that recolor after release, RD No. 11449, 24241, JP-A-61-201247
Bleach accelerator releasing couplers as described in U.S. Pat.
Examples thereof include ligand releasing couplers described in JP-A No. 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 the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027.

Specific examples of the high boiling point organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include phthalic acid esters (for example, dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate). , Bis (2,4-di-t-amylphenyl)
Phthalate, bis (2,4-di-t-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate), esters of phosphoric acid or phosphonic acid (eg, trifel phosphate, tricresyl phosphate, 2-ethylhexyldiphenylphosphate, tricyclohexylphosphate, tri-2-ethylhexylphosphate, tridecylphosphate, tributoxyethylphosphate and trichloropropylphosphate, di-2-ethylhexylphenylphosphonate),
Benzoic acid esters (for example, 2-ethylhexyl benzoate, dodecyl bendate, 2-ethylhexyl-p-hydroxybenzoate), amides (for example,
N, N-diethyldodecane amide, N, N-diethyllaurylamide, N-tetradecylpyrrolidone), alcohols or phenols (for example, isostearyl alcohol, 2,4-di-tert-amylphenol), aliphatic carvone Acid esters (eg, bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate), aniline derivatives (eg, N, N-dibutyl-2-butoxy-5-) tert-octylaniline), hydrocarbons (eg, paraffin, dodecylbenzene, diisopropylnaphthalene) and the like.
The auxiliary solvent has a boiling point of about 30 ° C or higher, preferably
An organic solvent having a temperature of 50 ° C. or higher and about 160 ° C. or lower can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate and dimethylformamide.

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

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

When the present invention is applied to a color photographic material, it can be applied to a light-sensitive material having various structures and a light-sensitive material obtained by combining a layer structure and a special color material.

A typical example thereof will be illustrated. Japanese Patent Publication No. 47-49031, Japanese Patent Publication No. 4
No. 9-3843, JP-B-50-21248, JP-A-59-58147,
JP-A-59-60437, JP-A-60-227256, JP-A-61-4
No. 043, JP-A-61-43743, JP-A-61-42657, etc., in which the coupling speed and diffusion of a color coupler are combined with the layer constitution. JP-B-49-15495 and U.S. Pat. No. 3,843,469, in which the same color-sensitive layer is divided into two or more layers, JP-B-53-37017, JP-B-53-37018,
JP-A-51-49027, JP-A-52-143016, JP-A-53-9
7424, JP-A-53-97831, JP-A-62-200350 and JP-A-59-177551, the arrangement of high-sensitivity layers and low-sensitivity layers and the arrangement of layers having different color sensitivities are specified. You can list things such as things.

Suitable supports that can be used in the present invention are, for example, those mentioned above.
RD.No. 17643, page 28, and RD.No. 18716, page 647 From the right column
See page 648, left column.

The color photographic light-sensitive material according to the present invention has the above-mentioned RD.No.
17643, pages 28 to 29, and No. 18716, 651, left column to right column, can be developed by a usual method.

The color developer used for the development processing of the light-sensitive material of the present invention,
An alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component is preferred. Aminophenol compounds are also useful as the color developing agent, but p-
A phenylenediamine compound is preferably used, and typical examples thereof include 3-methyl-4-amino-N, N-diethylaniline and 3-methyl-4-amino-N-ethyl-N.
-Β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N
Examples include -β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates. Two or more of these compounds can be used in combination depending on the purpose.

Color developing solutions include alkali metal carbonates, pH buffers such as borates or phosphates, bromide salts, iodide salts,
It is common to include a development inhibitor such as benzimidazoles, benzothiazoles or mercapto compounds, or an antifoggant. If necessary, such as hydroxyamine, diethylhydroxyamine, sulfite hydrazines, phenylsemicarbazide, triethanolamine, catecholsulfonic acid, and triethylenediamine (1,4-diazabicyclo [2,2,2] octane) Various preservatives, organic solvents such as ethylene glycol and diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts and amines, dye-forming couplers, competitive couplers, fogging agents such as sodium boron hydride , An auxiliary developing agent such as 1-phenyl-3-pyrazolidone, a viscosity-imparting agent, various chelating agents represented by aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid and phosphonocarboxylic acid, for example, ethylenediamine Tetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N , N, N ', N'-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof can be mentioned as representative examples.

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

The pH of these color developing solution and black-and-white developing solution is generally 9 to 12. The replenishment amount of these developers is
Although it depends on the color photographic light-sensitive material to be processed, it is generally 3 or less per 1 m 2 of the light-sensitive material and can be reduced to 500 ml or less by reducing the bromide ion concentration in the replenisher. When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air. Further, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developing solution.

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

The photographic emulsion tank after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further processing with two continuous bleach-fix baths,
The fixing treatment before the bleach-fixing treatment or the bleaching treatment after the bleach-fixing treatment can be optionally carried out according to the purpose.
Examples of bleaching agents include iron (III), cobalt (III),
Compounds of polyvalent metals such as chromium (VI) and copper (II), peracids, quinones, nitro compounds and the like are used. Typical examples of bleaching agents are ferricyanide; dichromate; iron (II
I) or cobalt (III) organic complex salts such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3
-Aminopolycarboxylic acids such as diaminopropane tetraacetic acid and glycol ether diamine tetraacetic acid or complex salts such as citric acid, tartaric acid and malic acid; persulfates; bromates; permanganates; nitrobenzenes and the like can be used. it can. Of these, aminopolycarboxylic acid iron (II) including ethylenediaminetetraacetic acid iron (III) complex salts
I) Complex salts and persulfates are preferable from the viewpoint of rapid processing and prevention of environmental pollution. Furthermore, iron (III) aminopolycarboxylate
Complex salts are particularly useful in both bleaching solutions and bleach-fixing solutions. The pH of the bleaching solution or the bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 5.5 to 8, but the processing can be carried out at a lower pH in order to speed up the processing.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath. Specific examples of useful bleach accelerators are described in the following specifications: US Pat. No. 3,893,858, West German Patents 1,290,812, 2,059,98.
No. 8, JP-A-53-32,736, JP-A-53-57,831 and JP-A-53-37,
418, 53-72,623, 53-95,630, 53-95,63
No. 1, 53-104,232, 53-124,424, 53-141,6
No. 23, No. 53-28,426, Research Disclosure
No. 17129 (July 1978) and the like, compounds having a mercapto group or a disulfide group; JP-A-50-140,12
No. 9 thiazolidine derivative; JP-B-45-8,506;
JP-A-52-20832, JP-A-53-32,735, U.S. Pat.
Thiourea derivatives described in 6,561; West German Patent No. 1,127,715
And iodide salts described in JP-A-58-16235; West German Patent No.
Polyoxyethylene compounds described in 966,410 and 2,748,430; polyamine compounds described in JP-B-45-8836;
Other JP-A-49-42,434, JP-A-49-59,644, JP-A-53-9
No. 4,927, No. 54-35,727, No. 55-26,506, No. 58-16
Compounds described in 3,940; bromide ions and the like can be used.
Among them, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of a large accelerating effect, and particularly, U.S. Pat. No. 3,893,858, West German Patent 1,290,812, JP-A-53-9.
The compounds described in 5,630 are preferred. In addition, US Patent No.
The compounds described in 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography.

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

The silver halide color photographic light-sensitive material of the present invention generally undergoes a washing and / or stabilizing step after desilvering. The amount of rinsing water in the rinsing step depends on the characteristics of the light-sensitive material (for example, depending on the material used such as a coupler), the purpose, and the rinsing water temperature.
It can be set in a wide range depending on the number of washing tanks (the number of stages), a replenishment system such as countercurrent and forward flow, and various other conditions. Of these, the relationship between the number of flushing tanks and the estimation in the multi-stage countercurrent system is described in the Journal of the Society of Motion Picture and T
It can be determined by the method described in elevision Engineers, Volume 64, P.248-253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above literature, the amount of washing water can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problem arises. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, calcium ions described in Japanese Patent Application No. 61-131,632,
The method of reducing magnesium ions can be used very effectively. Also, isothiazolone compounds and thiabendazoles described in JP-A-57-8542, chlorine-based disinfectants such as chlorinated sodium isocyanurate, and other benzotriazoles, etc. It is also possible to use disinfectants described in "Sterilization, disinfection and fungicide technology of microorganisms" edited by the Society of Sanitary Engineers, and "Dictionary of Disinfectants and Fungicides" by the Japan Society of Antifungals and Fungi.

The pH of washing water in the processing of the light-sensitive material of the present invention is 4-
9, preferably 5-8. The washing water temperature and washing time can be variously set depending on the characteristics of the light-sensitive material, application, etc., but in general, at 15-45 ° C for 20 seconds-10 minutes, preferably at 25-40 ° C.
A range of 30 seconds-5 minutes is selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such a stabilizing process, the method disclosed in
All known methods described in 57-8,543, 58-14,834 and 60-220,345 can be used.

Further, there is a case where a stabilizing treatment is further performed after the water washing treatment, and an example thereof is a stabilizing bath containing formalin and a surfactant, which is used as a final bath of a color light-sensitive material for photographing. . Various chelating agents and fungicides can also be added to this stabilizing bath.

The overflow solution accompanying the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up the processing.
For incorporation, it is preferable to use various precursors of color developing agents. For example, indaniline compounds described in U.S. Pat.No. 3,342,597, No. 3,342,599, Schiff's base type compounds described in Research Disclosures 14,850 and 15,159, aldol compounds described in No. 13,924, metals described in U.S. Pat. Examples thereof include salt complexes and urethane compounds described in JP-A-53-135,628.

The silver halide color photographic material of the present invention contains various 1-phenyl-photographic compounds for the purpose of promoting color development, if necessary.
You may incorporate 3-pyrazolidones. Typical compounds are JP-A Nos. 56-64,339, 57-144,547, and 58.
-115,438, etc.

The 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 a higher temperature accelerates the processing to shorten the processing time, and a lower temperature lowers the image quality to improve the stability of the processing liquid. be able to. Further, in order to save silver in the light-sensitive material, processing using cobalt intensification or hydrogen peroxide intensification described in West German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be performed.

Further, the silver halide light-sensitive material of the present invention is described in US Pat.
500,626, JP-A-60-133449, 59-218443, 6
It can also be applied to the photothermographic materials described in 1-238056 and European Patent 210,660A2.

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

Example-1 The present invention will be described in comparison with a comparative example.

(Manufacturing method of Em-A) 1000 ml of an aqueous solution containing 40 g of gelatin and 0.2 g of KBr is heated to 75 ° C.
With vigorous stirring. 208 ml of silver nitrate aqueous solution (AgNO ₃ 1.46
g) and 208 ml of KBr aqueous solution (1.1 g of KBr) were added simultaneously over 17 minutes. The silver potential of the reaction solution was adjusted to -25 mV with respect to a saturated calomel electrode, and then thiourea dioxide (0.6 mg) was added as an aqueous solution. Thereafter, an aqueous silver nitrate solution 471 ml (AgNO ₃ 9
4.2g) and KBr aqueous solution (KBr, 14.6% by weight) simultaneously over 33 minutes, maintaining the silver potential of the reaction solution at −25 mV at an initial flow rate of 1 ml / min and a final flow rate of 19 ml / min. Was added. After completion of the addition, the mixture was aged for 10 minutes and then desalted by flocculation. Add gelatin 43g, 40 ℃
The pH was adjusted to 6.9 and pAg8.0 to adjust the yield to 700 g. At 60 ° C, potassium thiocyanate 3.0 × 10 ^-3 mol / mol Ag, sodium thiosulfate 3.0 × 10 ^-5 mol / mol Ag, and potassium chloroaurate 1.2 × 10 ^-6 mol / mol Ag were added and stirred for 40 minutes. It was sensitized with gold-sulfur and designated as Em-A. The resulting emulsion was monodisperse octahedral grains having an average equivalent circle diameter of 0.60 μm and a variation coefficient of the equivalent circle diameter of 9%.

(Manufacturing method of Em-B) In the manufacturing method of Em-A, (NH ₄ ) ₂ was added for 3 minutes from 20 minutes after the start of addition of the second-stage silver nitrate aqueous solution to 10 minutes before the end.
PdCl ₄ 4 × 10 ^-4 mol / mol Ag and potassium thiocyanate 2 ×
Em-B was prepared in the same manner as Em-A except that 10 ⁻³ mol / mol Ag was added.

(Manufacturing method of Em-C) In the manufacturing method of Em-A, (NH ₄ ) ₂ PdCl ₄ 4 × 10 ⁻⁴ mol / mol Ag was added 10 minutes before the addition of the gold-sulfur sensitizer during gold-sulfur sensitization. And potassium thiocyanate were added in the same manner as Em-A except that 2 × 10 ⁻³ mol / mol Ag was added to obtain Em-C.

(Manufacturing method of Em-D) Em-A was dissolved at 40 ° C., and (NH ₄ ) ₂ PdCl ₄ 4 × 10 ⁻⁴ mol /
Mol Ag and potassium thiocyanate 2 × 10 ⁻³ mol / mol Ag were added and stirred for 30 minutes to give Em-D.

(Manufacturing method of Em-E) In the manufacturing method of Em-A, (NH ₄ ) ₂ PdCl ₄ 4 × 10 ⁻⁴ mol / mol Ag and potassium thiocyanate 2 × 10 2 minutes after the addition of the second-stage silver nitrate aqueous solution is completed. ^-3 mol / mol Ag was added, stirred for 8 minutes, and then desalted by the flocculation method.
Em-E was prepared in the same manner as Em-A.

(Manufacturing method of Em-F) Immediately before desalting by the flocculation method in the manufacturing method of Em-A, (NH ₄ ) ₂ PdCl ₄ 4 × 10 ⁻⁴ mol / mol Ag and potassium thiocyanate 2 × 10 ⁻³ mol / Mole Ag except
It was adjusted in the same manner as Em-A and designated as Em-F.

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

After leaving these samples under conditions of 40 ° C and 70% relative temperature for 14 hours, they were exposed through a continuous wedge for 1/100 seconds,
The following color development processing was performed.

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

Process Processing time Processing temperature Color development 2 minutes 00 seconds 40 ° C Bleaching fixing 3 minutes 00 seconds 40 ° C Water washing (1) 20 seconds 35 ° C Water washing (2) 20 seconds 35 ° C Stability 20 seconds 35 ° C Drying 50 seconds 65 ° C Next, the composition of the treatment liquid will be described.

(Color developer) (Unit: g) Diethylenetriaminepentaacetic acid 2.0 1-Hydroxyethylidene-1,1-diphosphonic acid 3.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1.5 mg Hydroxylamine sulfate 2.4 4- [N- Ethyl-N-β-hydroxyethylamino] -2-methylaniline sulfate 4.5 Water was added to 1.0 L pH 10.05 (Washing liquid) Tap water is passed through a mixed bed column filled with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH type anion exchange resin (Amberlite IR-400). Water was added to treat calcium and magnesium ions at a concentration of 3 mg / L or less, and then 20 mg / L of sodium diisocyanurate dichloride and 1.5 g / L of sodium sulfate were added.

 This solution has a pH in the range 6.5-7.5.

(Stabilizer) (Unit: g) Formalin (37%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether 0.3 (Average degree of polymerization 10) Ethylenediaminetetraacetic acid disodium salt 0.05 Water added 1.0L pH 5.0-8.0 Sensitivity Is the relative value of the reciprocal of the exposure dose expressed in lux · second at a density of 0.2 on the fog.

 The results are summarized in Table 2.

As is clear from Table 2, low fog and high sensitivity were achieved only by adding the palladium compound after the grain formation step of the present invention and before the desalting step. No image was obtained when a palladium compound was added during grain formation (Em-B).

The Em-A and Em-E repeatedly prepared 3 times each, respectively and _{Em-A 1, A 2,} A 3 and _{Em-E 1, E 2,} E 3, similarly coated, exposed and developed the The results shown in Table 3 were obtained.

As is clear from Table 3, the reproducibility of the emulsion is remarkably improved by adding the palladium compound after the grain forming step of the present invention and before the desalting step. That is, the production of silver halide photographic emulsion is stabilized.

In the process for producing Em-C and Em-E, Em-C and Em-E were prepared by changing the time required for flow curation, and Em-C ₁ , C ₂ and Em-E ₄ , E ₅ were prepared in the same manner. The results shown in Table 4 were obtained by coating, exposing and developing.

As is clear from Table 4, by adding the palladium compound after the completion of the grain forming step of the present invention and before the desalting step, the reproducibility of the emulsion is extremely improved regardless of the time required for flocculation. You can see that That is, a stabilized production method of a silver halide photographic emulsion could be achieved.

Example-2 The dependency of the addition amount of the palladium compound will be described.

(Manufacturing method of Em-G) Water solubility including gelatin and KBr is kept at 40 ℃, and under constant stirring, silver nitrate aqueous solution (AgNO ₃ , 32.7 g) and halogen solution (KBr, 24.9 g, KI, 1.3 g) 4 Added over minutes. KBr,
After adding an aqueous solution containing gelatin, the temperature was raised to 70 ° C., and then an aqueous solution containing 6 mg of dimethylamine borane and
Compound 1-2 in the table was added at the same time as an aqueous solution containing 100 mg. Thereafter, an aqueous silver nitrate solution (AgNO ₃ , 152.3 g) and an aqueous halogen solution (containing 53% by weight of KI with respect to KBr) were added over 32.1 minutes. At this time, the silver potential of the reaction solution was kept at 0 mV with respect to the saturated calomel electrode. After that, an aqueous silver nitrate solution (AgNO ₃ ,
7.2 g) and aqueous NaCl solution (NaCl, 6.7 g) were added over 1.5 minutes. Five minutes after the completion of the addition, desalting was performed by a flocculation method. Gelatin was added and adjusted to pH 6.9 and pAg 8.0 at 40 ° C. This emulsion has an average thickness of 0.13 μm, an average equivalent circle diameter of 0.68 μm, a coefficient of variation of equivalent circle diameter of 28%, and an aspect ratio of 5.
It was 2 tabular grains.

The following sensitizing dye A was added to this emulsion 1.40 × 10 ^-3 (sensitizing dye A) After adding mol / mol Ag, potassium thiocyanate 3.0 × 10 ⁻³ mol / mol Ag, sodium thiosulfate 4.8 × at 64 ° C.
10 ^-5 mol / mol Ag, and potassium chloroaurate 1.0 × 10 ^-6
Mol / mol Ag was added and stirred for 40 minutes, the following antifoggant A was added at 5 × 10 ⁻⁴ mol / mol Ag, and the temperature was lowered. (Antifoggant A) Em-G.

(Manufacturing method of Em-H) In the manufacturing method of Em-G, (NH ₄ ) ₂ PdCl ₄ 1 × 10 ⁻⁵ mol / mol Ag and potassium thiocyanate 5 × 10 ⁻⁵ mol / mol 30 seconds after the addition of silver nitrate was completed. After adding Ag and stirring for 5 minutes, it was prepared in the same manner as Em-G except that desalting was performed by a flocculation method to obtain Em-H.

(Manufacturing method of Em-I) In the manufacturing method of Em-G, 30 seconds after the end of addition of silver nitrate, (NH ₄ ) ₂ PdCl ₄ 5 × 10 ⁻⁵ mol / mol Ag and potassium thiocyanate 2.5 × 10 ⁻⁴ mol / mol After adding Ag and stirring for 5 minutes, it was prepared in the same manner as Em-G except that it was desalted by the flocculation method to obtain Em-I.

(Production method of Em-J) In the production method of Em-G, 30 seconds after the addition of silver nitrate was completed, (NH ₄ ) ₂ PdCl ₄ 1 × 10 ⁻⁴ mol / mol Ag and potassium thiocyanate 5 × 10 ⁻⁴ mol / mol After adding Ag and stirring for 5 minutes, it was prepared in the same manner as Em-G except that desalting was carried out by the flocculation method to obtain Em-J.

(Manufacturing method of Em-K) In the manufacturing method of Em-G, 30 seconds after the addition of silver nitrate was completed, (NH ₄ ) ₂ PdCl ₄ 4 × 10 ⁻⁴ mol / mol Ag and potassium thiocyanate 2 × 10 ⁻³ mol / mol After adding Ag and stirring for 5 minutes, it was prepared in the same manner as Em-G except that it was desalted by a flocculation method to obtain Em-K.

(Manufacturing method of Em-L) In the manufacturing method of Em-I, 10 minutes before adding the gold-sulfur sensitizer at the time of sensitizing gold-sulfur, (NH ₄ ) ₂ PdCl ₄ 5 × 10 ⁻⁴ mol / mol
Em-L was prepared in the same manner as Em-I except that Ag and potassium thiocyanate 2.5 × 10 ⁻³ mol / mol Ag were added.

The coating aids Em-G to L and a hardening agent were added, and the mixture was coated on a cellulose triacetate film base so that Ag was 2 g / m ² . The coated emulsion was exposed to a tungsten bulb (color temperature 2854K) through a continuous wedge for 1 second. The exposed coating emulsion was prepared by using the following surface developer (MAA-1) at 1
Developed for 0 minutes.

Metol 2.5 g d-Ascorbic acid 10.0 g Potassium bromide 1.0 g Nabox 35.0 g Water 1000 ml The sensitivity of the emulsion obtained is indicated by the relative value of the reciprocal of the exposure dose required for the optical density to become fogging plus 0.1. It was

 The results obtained are shown in Table 5.

As is apparent from Table 3, high sensitivity was achieved with low fog by adding the palladium compound after the grain formation step and before the desalting step by adding 5 × 10 ⁻⁵ mol or more per mol of silver halide. .

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

On the undercoated cellulose triacetate film support, a sample which is a multi-layer color light-sensitive material having each layer having the following composition was prepared.

The amount coated amount (Composition of photosensitive layer) is represented in units of g / m ² of silver for silver halide and colloidal silver, also couplers, the amount for the additives and gelatin, expressed in units of g / m ^2, The sensitizing dye is shown by the number of moles per mole of silver halide in the same layer. The symbols indicating additives have the following meanings. However, when there are multiple utilities, one of them is listed as a representative.

UV; UV absorber, Solv; high boiling organic solvent, ExF; dye,
ExS: Sensitizing dye, ExC: Cyan coupler, ExM: Magenta coupler, ExY: Yellow coupler, Cpd; Additive first layer (antihalation layer) Black colloidal silver 0.15 Gelatin 2.9 UV-1 0.03 UV-2 0.06 UV-3 0.07 Solv-2 0.08 ExF-1 0.01 ExF-2 0.01 Second layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, uniform AgI type, equivalent circle diameter of 0.
6 μm, thickness 0.2 μm, variation coefficient of equivalent circle diameter 37%, tabular grain, diameter / thickness ratio 3.0) Coating silver amount 0.4 Gelatin 0.8 ExS-1 6.9 × 10 ^-4 ExS-2 5.2 × 10 ^-4 ExS-5 6.9 × 10 ^-4 ExS-7 2.4 × 10 ^-5 ExC-1 0.17 ExC-2 0.03 ExC-3 0.13 Third layer (medium-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 6 mol%, core-shell ratio 2: 1 internal high AgI type, sphere equivalent diameter 0.65 μm, variation coefficient of sphere equivalent diameter 25
%, Plate-like grain, diameter / thickness ratio 2.0) Coating silver amount 0.65 Silver iodobromide emulsion (AgI 4 mol%, uniform AgI type, spherical equivalent diameter 0.
4 [mu] m, spherical coefficient of variation of 37% equivalent diameter, the plate-like particles, diameter / thickness ratio 2.0) coating silver amount 0.1 Gelatin ^{1.0 ExS-1 2 × 10 -4} ExS-2 1.2 × 10 -4 ExS-5 2 × 10 - ⁴ ExS-7 7 × 10 ^-6 ExC-1 0.31 ExC-2 0.01 ExC-3 0.06 4th layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 6 mol%, core-shell ratio 2: 1 inside) High AgI type, sphere equivalent diameter 0.7 μm, variation coefficient of sphere equivalent diameter 25%,
Plate-shaped particles, diameter / thickness ratio 2.5) Silver coating amount 0.9 Gelatin 0.8 ExS-1 1.6 × 10 ^-4 ExS-2 1.6 × 10 ^-4 ExS-5 1.6 × 10 ^-4 ExS-7 6 × 10 ^-4 ExC- 1 0.07 ExC-2 0.05 Solv-1 0.07 Solv-2 0.20 Cpd-7 4.6 × 10 ^-4 Fifth layer (intermediate layer) Gelatin 0.6 UV-4 0.03 UV-5 0.04 Cpd-1 0.1 Polyethyl acrylate latex 0.08 Solv- 1 0.05 6th layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, uniform AgI type, equivalent spherical diameter of 0.
4 [mu] m, spherical coefficient of variation of 37% equivalent diameter, the plate-like particles, diameter / thickness ratio 2.0) coating silver amount 0.18 Gelatin ^{0.4 ExS-3 2 × 10 -4} ExS-4 7 × 10 -4 ExS-5 1 × 10 - ⁴ ExM-5 0.11 ExM-7 0.03 ExY-8 0.01 Solv-1 0.09 Solv-4 0.01 7th layer (medium sensitivity green emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, surface with core-shell ratio 1: 1) High AgI type, circle equivalent diameter 1.0 μm, thickness 0.2 μm, variation coefficient of circle equivalent diameter 15%, tabular grain, diameter / thickness ratio 5.0) Coating silver amount 0.27 Gelatin 0.6 ExS-3 4 × 10 ^-4 ExS-4 1.4 × 10 ^-3 ExS-5 2 × 10 ^-4 ExM-5 0.17 ExM-7 0.04 ExY-8 0.02 Solv-1 0.14 Solv-4 0.02 Eighth layer (high sensitivity green emulsion layer) Silver iodobromide emulsion (AgI 8.7 mol%, silver ratio 3: 4: 2 from the inside
Multi-layered particles of, AgI content from the inside 24 mol, 0 mol,
3 mol%, equivalent sphere diameter 0.7 μm, coefficient of variation of equivalent sphere diameter 25
%, Plate-like particles, diameter / thickness ratio 1.6) Coating amount 0.7 Gelatin 0.8 ExS-4 5.2 × 10 ^-4 ExS-5 1 × 10 ^-4 ExS-8 0.3 × 10 ^-4 ExM-5 0.1 ExM-6 0.03 ExY-8 0.02 ExC-1 0.02 ExC-4 0.01 Solv-1 0.25 Solv-2 0.06 Solv-4 0.01 Cpd-7 1 × 10 ^-4 9th layer (intermediate layer) Gelatin 0.6 Cdp-1 0.04 Polyethyl acrylate latex 0.12 solv-1 0.02 10th layer (donor layer for multi-layer effect on red-sensitive layer) Silver iodobromide emulsion (AgI 6 mol%, internal high AgI type with core-shell ratio 2: 1, sphere equivalent diameter 0.7 μm, sphere equivalent diameter Coefficient of variation 25%,
Plate-like grains, diameter / thickness ratio of 2.0) Coating silver amount 0.68 Silver iodobromide emulsion (AgI 4 mol%, uniform AgI type, equivalent spherical diameter 0.
4 μm, variation coefficient of equivalent spherical diameter 37%, plate-like particles, diameter / thickness ratio 2.5) Coating silver amount 0.19 Gelatin 1.0 ExS-3 6 × 10 ^-4 ExM-10 0.19 Solv-1 0.20 11th layer (yellow filter layer) ) Yellow colloidal silver 0.06 Gelatin 0.8 Cpd-2 0.13 Solv-1 0.13 Cpd-1 0.07 Cpd-6 0.002 H-1 0.13 12th layer (low sensitivity blue emulsion layer) Em-G to L Coating amount 0.45 Gelatin 1.8 ExC -1 0.06 ExC-4 0.03 ExY-9 0.14 ExY-11 0.89 Solv-1 0.42 13th layer (intermediate layer) Gelatin 0.7 ExY-12 0.20 Solv-1 0.34 14th layer (high sensitivity blue-sensitive emulsion layer) Salt iodine Silver halide emulsion (AgI 10 mol%, internal high AgI type, AgCl
7 mol%, inner shell AgCl type, circle equivalent diameter 2.0 μm, thickness 0.3 μ
m, coefficient of variation of equivalent circle diameter 30%, tabular grain, diameter / thickness ratio
7.0) Coating silver amount 0.5 Gelatin 0.5 ExS-6 7 × 10 ^-4 ExS-9 0.01 ExY-11 0.20 ExC-1 0.02 Solv-1 0.10 15th layer (1st protective layer) Fine grain silver iodobromide emulsion (AgI 2 Mol%, uniform AgI type, equivalent spherical diameter 0.07 μm) Coating silver amount 0.12 Gelatin 0.9 UV-4 0.11 UV-5 0.16 Solv-5 0.02 H-1 0.13 Cpd-5 0.10 Polyethyl acrylate latex 0.09 16th layer (2nd layer) Protective layer) Fine grain silver iodobromide emulsion (AgI 2 mol%, uniform AgI type, spherical equivalent diameter 0.07 μm) Coating silver amount 0.36 Gelatin 0.55 Polymethylmethacrylate particles (diameter 1.5 μm) 0.2 H-1 0.17 In addition to the ingredients, emulsion stabilizer Cpd-3
(0.07 g / m ² ) and the surfactant Cpd-4 (0.03 g / m ² ) were added as coating aids.

In addition, in order to stabilize processability and film physical properties, SPC-
1, SPC-2 was added. The structural formula of the compound used is represented by
Shown in the table.

The samples using Em-G, H, I, J, K, and L prepared in Example-2 for the 12th layer were samples 301, 302, 303, 304, 305, and 3, respectively.
It was 06.

After exposing the color photographic light-sensitive materials 301 to 306 as described above, they were processed by an automatic processor by the method described below (until the cumulative replenishment amount of the bleaching solution became 3 times the capacity of the mother liquor tank).

Next, the composition of the treatment liquid will be described.

(Washing solution) Common for mother liquor and replenisher Tap water mixed with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH type anion exchange resin (Amberlite IR-400). Water was passed through the bed-type column to treat calcium and magnesium ions at a concentration of 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.

About the characteristic curve of the yellow color image, from fog density to 1.0
The sensitivity was shown by the 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 the palladium compound after the grain formation step and before the desalting step by 5 × 10 ⁻⁵ mol or more per mol of silver halide.

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

Claims (1)

(57) [Claims] 1. A method for producing a silver halide photographic emulsion comprising the steps of grain formation, desalting and chemical sensitization, and after completion of the grain formation step of silver halide grains which have been reduction sensitized in the grain formation step, A method for producing a silver halide photographic emulsion, which comprises adding 5 × 10 ⁻⁵ mol or more of a palladium compound per mol of silver halide before the desalting step.