JPH07209794A - Silver halide emulsion - Google Patents

Abstract

PURPOSE:To provide the emulsion containing flat silver halide grains high in silver chloride content superior in rapid processing aptitude and restrained from fog and improved in preservable property and having principal faces (100). CONSTITUTION:The silver halide emulsion layer contains the flat silver halide grains having 2 parallel principal faces (100) and an aspect ratio of >=5, in an amount of >=50% of the projection areas of the total silver halide grains and it contains the compound represented by the formula in which R<1> is H or 1-6C alkyl; R<2> is II, optionally substituted 1-6C alkyl, such alkenyl, or the like, and when n is >=2, each of (R<2>)n may be same or different or each may combine with each other to form a condensed ring; R<3> is H, optionally substituted alkyl or such alkenyl, or such aralkyl; X is an anion; and n is 0, 1, 2, or 3.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide emulsion, and in an emulsion containing a high silver chloride excellent in rapid processability,
Particularly, it relates to a silver halide emulsion excellent in photographic sensitivity, gradation and storage stability.

[0002]

2. Description of the Related Art Recently, photographic light-sensitive materials are required to have various performances, but tabular grains are suitable as silver halide photographic emulsion grains in view of sensitivity, graininess, sharpness and color sensitization efficiency. It is well known to those skilled in the art. As tabular silver halide emulsion grains, tabular grains having a high crystallinity of silver bromide, which have twin planes and whose main plane is the (111) plane, are often used. However, when the amount of the sensitizing dye to be adsorbed on the silver halide grains is increased, the inherent desensitization becomes large. In contrast,
It is known that particles having a (100) plane usually have good color sensitizing properties. Therefore, it is desired to develop a tabular silver halide emulsion grain having a main plane of (100) plane and to increase its sensitivity.

Regarding tabular silver halide grains whose main plane is the (100) plane, and grains having a high silver bromide content,
A.MIGNOT, E.FRANCOIS AND M.CATINAT, "CRISTAUX DE
RBOMURE D'ARGENT PLATS, LIMITES PAR DES FACES (100)
ET NON MACLES ", Journal of Crystal Growth 123
(1974) 207-213, JP-A-51-88
No. 017 and Japanese Patent Publication No. 64-8323.

Recently, there has been a strong demand for simplifying and speeding up the development process and for lowering the replenishment rate of the processing solution. For such requirements, it is advantageous to use silver halide grains having a high solubility and high silver chloride content. Regarding tabular grains having a high silver chloride content and a principal plane consisting of a (100) plane, European Patent 0534395A1 and US Pat.
4337 and the like. However, such a tabular (100) high silver chloride emulsion has a higher solubility of silver salt than a tabular (iodo) silver bromide emulsion whose main plane is the (111) plane, which has been often used conventionally. The pAg is low, and the (100) plane is generally more likely to be fogged than the (111) plane. Also, fog during storage and sensitivity and gradation change are likely to occur. Therefore, these improvements have been desired without impairing the color sensitizing property and the development progressing property.

[0005]

DISCLOSURE OF THE INVENTION The present invention provides an emulsion containing high silver chloride grains which is excellent in rapid processability and has low color sensitization sensitivity, gradation and particularly fog and excellent storage stability (1).
It is to provide a tabular silver halide emulsion having a (00) plane as a main plane.

[0006]

The above-mentioned objects of the present invention have been achieved by the following. (1) The two parallel main planes are (100) planes, the aspect ratio is 1.5 or more, and the silver chloride content of the grains is 6
A tabular silver halide grain having a content of 0 mol% or more occupies 50% or more of the projected area of all grains and contains a compound of the following general formula (I). .

[0007]

[Chemical 2]

In the formula, R ¹ is a hydrogen atom or a carbon number of 1 to
An alkyl group having 6 carbon atoms, R ² is a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, an alkenyl group,
It is an alkynyl group or an alkoxy group, or an electron withdrawing group, and when n is 2 or more, a plurality of R ² may be the same or different, and R ² may be linked to each other to form a condensed ring. . R ³ is a hydrogen atom or an optionally substituted alkyl group, alkenyl group, or aralkyl group, X ⁻ is an anion, and n is 0 or 1 to 3. More preferably, it is achieved by the silver halide emulsion described in (1) above, which further contains at least one mercaptotetrazole.

A detailed description of the compounds of general formula (I) according to the present invention is given. The alkyl group represented by R ¹ has a carbon number of 1 to 6, and examples thereof include a methyl group and a propyl group. Examples of the alkyl group having 1 to 6 carbon atoms, alkenyl group, alkynyl group and alkoxy group represented by R ² include methyl group, ethyl group, hexyl group, allyl group, propargyl group and methoxy group. Examples of the groups substitutable for these groups include a hydroxyl group, a carboxyl group, an amino group, a carbamoyl group, a sulfamoyl group, and a halogen atom.

The electron withdrawing group represented by R ₂ is
Halogen atom (eg Cl), carboxyl group, trifluoromethyl group, cyano group, nitro group, —SO ₂ R ⁴
A sulfo group, an -SO ₂ NHR ⁴ aminosulfonyl group,
There is an aminocarbonyl group of —CONHR ⁴ and an acyl group of —COR ⁴ (R ⁴ represents a hydrogen atom, a lower alkyl or a phenyl group). When a plurality of R ^2's are linked to each other to form a condensed ring, for example, the general formula (I) is naphthothiazonium.

Examples of the alkyl group, alkenyl group and aralkyl group represented by R ³ include methyl group, propyl group, butyl group, hexyl group, allyl group and benzyl group. Examples of the group substituted with these include a carboxyl group, a sulfone group, a hydroxyl group, an amino group, and a halogen atom. The anion represented by X ⁻ is, for example, a halide ion, a nitrate ion, a phosphate ion, a chlorate ion, or an anion derived from an organic acid, such as a formate (formate) ion, an acetate (acetic acid) ion or p-. Toluene sulfonate (PTS) ion is mentioned. However, when R ^{1 to} R ³ have an anionic group, X ⁻ is not necessary. General formula (I)
Specific examples of the following include the following compounds.

[0012]

[Chemical 3]

[0013]

[Chemical 4]

[0014]

[Chemical 5]

In the present invention, at least one mercaptotetrazole is preferably used in combination with the compound of the general formula (I), and more preferably 1-phenyl-5 of the following general formula (II). -A mercaptotetrazole or a salt thereof (for example, sodium salt, ammonium salt, calcium salt, etc.).

[0016]

[Chemical 6]

In the formula, m is an integer of 1 to 3 and R
⁵ is a hydrogen atom, a lower alkyl group, a sulfonic group, a halogen atom (e.g. _{Cl), - SO 2 NH 2} , -NHR
⁶ groups, -NHCOR ⁶ group, -CONHR ⁶ group, -NHC
ONHR ⁶ group, -OR ⁶ group, -COOR ⁶ group, -OCO
R ⁶ groups, (R ⁶ is a hydrogen atom or a lower alkyl, a phenyl group) nitro group, a cyano group, a trifluoromethyl group, and the like, when m is 2 or more, plural R ₅ may be different in the same You may

A specific compound of the general formula (II) is the case where R ⁵ of the general formula (II) is as follows (compounds II-6, II-
Other than 12, m in the general formula (II) is 1. In addition, (o), (m) and (p) in the compound examples represent that the substitution positions are the ortho, meta and para positions, respectively. ). II-1 H II-2 ( m) -COOH II-3 (m) -SO 3 Na II-4 (m) -NHCONHCH 3 II-5 (m) -NHCOCH 3 II-6 (o) -OH, ( p) -COOH II-7 (p ) -SO 2 NH 2 II-8 (m) -NHCOC 5 H 11 II-9 (p) -OCH 2 CH 2 OH II-10 (m) -NHCONHC 4 H 9 II -11 (p) -COO- (ph) (ph represents a phenyl group) II-12 (o) -Cl, (p) -Cl

The silver halide emulsion of the present invention will be described below. The tabular silver halide grains having a silver chloride content of 60 mol% or more (hereinafter sometimes referred to as tabular grains) having a (100) plane as a main plane used in the present invention have a silver chloride content of It is preferably 75 mol% or more, more preferably 90 mol% or more, and most preferably 95 mol%.
That is all.

The silver halide emulsion used in the present invention is a silver halide emulsion containing at least a dispersion medium and the above-mentioned silver halide grains, and 50% of the total projected area of all silver halide grains in the emulsion. As described above, more preferably 60% or more is a tabular silver halide grain having a main plane of (100) plane. The term "projected area" as used herein means the projected area of silver halide emulsion grains when they are arranged on a substrate in a state where they do not overlap each other and tabular grains are arranged such that the principal planes thereof are parallel to the substrate surface. Further, the principal plane refers to two parallel maximum outer surfaces in one tabular grain. The aspect ratio (diameter / thickness) of this tabular grain is 1.5 or more, preferably 2 or more, more preferably 3 to 25, and further preferably 3 to 15. Here, the diameter means the diameter of a circle having an area equal to the projected area of the particle when the particle is observed with an electron microscope. The thickness means the distance between the main planes of tabular grains. The tabular silver halide grains have a diameter of preferably 10 μm or less, more preferably 0.2 to 5 μm, still more preferably 0.2 to 3 μm. The thickness is preferably 0.7 μm or less, more preferably 0.03 to 0.3 μm, and further preferably 0.05 to 0.2 μm. The grain size distribution of the tabular grains is preferably monodisperse, and the coefficient of variation is preferably 40% or less, more preferably 20% or less.

The "principal plane" is defined as a set of parallel planes having the largest area among the crystal surfaces forming substantially rectangular parallelepiped emulsion grains, and the fact that the principal plane is the (100) plane is determined by electron diffraction. Method or X-ray diffraction method. A substantially rectangular parallelepiped emulsion grain means that the main plane is (100)
Although it is formed from a plane, it may have (111) crystal faces from 1 to 8. That is, a rectangular parallelepiped 8
One to eight of the four corners may have a sharpened shape.

The two parallel main planes used in the present invention are (100) planes, and the silver chloride content of the grains is 60 mol%.
Emulsions containing high silver chloride tabular grains described above are described in European Patent No. 0,534,395A1 and US Pat. No. 5,264,337, or Japanese Patent Application No. 5-96250.
It can be prepared according to the method described below in No. From the viewpoint of production stability and monodispersity of particle size, the method described in Japanese Patent Application No. 5-96250 is preferable. 1) Nucleation process The tabular nuclei, which are the nuclei of tabular grains, have a high production ratio under the condition that the introduction of lattice defects easily occurs. As a method for obtaining plate nuclei with high reproducibility and a high production ratio, a method utilizing halogen conversion of product nuclei is effective. In this method, first, silver halide nucleation is performed, and subsequently, a halogen ion which forms a more insoluble silver halide is introduced to perform halogen conversion. More specifically, the halogen composition structure of the nucleus formed during nucleation has, for example, a structure of (AgX ₁ | AgX ₂ ) or (AgX ₁ | AgX ₄ | AgX ₃ ). This structure can be formed, for example, by simultaneously adding a silver salt aqueous solution and a halide salt aqueous solution and changing the halogen composition of the halide aqueous solution discontinuously.
Alternatively, an aqueous solution of a halide salt is added to the dispersion medium solution, then an aqueous solution of a silver salt is added to form AgX ₁ , then another aqueous solution of a halide salt is added, and then an aqueous solution of a silver salt is added, ( An AgX ₁ | AgX ₂ ) structure can be prepared, or a combination thereof can be prepared.

AgX₁And AgX₂And AgX₁And Ag
X_Four, AgX_FourAnd AgX₃Is Cl^-Content or Br^-
The content is 25 to 100 mol%, preferably 50 to 100 mol%.
%, More preferably 75-100 mol%.
Further Cl^-Content or Br ^-In addition to the content difference, or
I^-Content is 5 to 100 mol%, preferably 10 to 100
Mol%, more preferably 30-100 mol%
It Others, Cl^-Difference in content or Br^-The content difference is the above
Follow the rules, I^-A mode in which the content difference is 0 to 5 mol%
Can be mentioned. (AgX₁| AgX₂) In case of
AgX₁: AgX₂Molar ratio of (AgX₁｜ Ag
X_Four| AgX₃) AgX₁: AgX₂: AgX₃Mo
The various ratios can be changed to obtain the most preferable embodiment of the present invention.
The molar ratio can be selected and used.

Circle-Equivalent Projected Grain of Core Grain of Tabular Grain
The child diameter is preferably 0.15 μm or less, and 0.02 to
0.1 μm is more preferable, and 0.01 to 0.1 μm is more preferable.
Is preferred. The dispersion medium concentration of the dispersion medium solution at the time of nucleation was 0.
01 to 10% by weight is preferable, 0.02 to 5% by weight
More preferable. The pH is preferably 1-10, more preferably 2-9.
preferable. The temperature is preferably 10 to 80 ° C, and 30 to 60
C is more preferred. Excess Br ^-Concentration is 10^-2Mol / L or less
Lower preferred, 10^-2.5It is more preferably at most mol / L.
Excess Cl^-The concentration is preferably pCl = 0.8 to 3.0,
1.2-2.8 are more preferable.

At the time of nucleation, a dispersion medium can be included in the silver salt aqueous solution and / or the halide salt aqueous solution added to enable uniform nucleation. The dispersion medium concentration is preferably 0.01% by weight or more, more preferably 0.02 to 2% by weight, still more preferably 0.05 to 1% by weight. A low molecular weight gelatin having a molecular weight of 3,000 to 60,000, preferably 8,000 to 40,000 is more preferable. Furthermore, it is more preferable that the aqueous solution of silver salt and the aqueous solution of halide salt are directly added to the liquid through a porous material addition system having 3 to 10 ¹⁵ , preferably 30 to 10 ¹⁵ pores. For details, see Japanese Patent Laid-Open No. 3-
No. 21339, No. 4-193336, and Japanese Patent Application No. 4-24
The description of No. 0283 can be referred to. Gelatin having a lower methionine content has a higher frequency of defect formation. From the gelatin having a methionine content of 1 to 60 μmol / g, the most preferable gelatin can be selected and used according to each case. By lowering the concentration of excess halogen ions or the concentration of excess silver ions at the time of nucleation, the mixing ratio of twin grains can be reduced.

A silver salt aqueous solution and a halide salt aqueous solution are added by a simultaneous mixing method to a dispersion medium solution containing at least a dispersion medium and water with stirring to form nuclei. The Cl ⁻ concentration in the dispersion medium solution during nucleation is preferably 10 ^−1.5 mol / liter or less, and the silver ion concentration is preferably 10 ⁻² mol / liter or less. The pH is preferably 2 or more, more preferably 5 to 10. The gelatin concentration is preferably 0.01 to 3% by weight,
0.03 to 2% by weight is more preferable.

The temperature during nucleation is not limited, but usually 1
0 degreeC-80 degreeC is preferable, and 20-70 degreeC is more preferable. The addition rate of the silver salt aqueous solution is preferably 0.3 to 20 g / min, and more preferably 0.5 to 15 g / min, per liter of the container solution. The pH of the container solution is not particularly limited, but usually pH 1 to 11, preferably pH 3 to 10 is used. The most preferable pH value can be selected and used according to the combination of excess silver ion concentration, temperature, and the like.

It is preferable that substantially no NH ₃ coexist in the nucleation process. Here, “substantially” means that the silver halide solvent concentration d ₀ is preferably d ₀ ≦ 0.5 mol / liter, more preferably d ₀ <0.1 mol / liter, and further preferably d ₀ <0.02. Refers to mol / liter. It is preferable that substantially no silver halide solvent other than NH ₃ is allowed to coexist in the nucleation and growth processes. Here, “substantially” means the same as the d ₁ concentration regulation. As a silver halide solvent other than NH ₃ , thioethers, thioureas,
Antifoggants such as thiocyanates, organic amine compounds and tetrazaindene compounds can be mentioned, and thioethers, thioureas and thiocyanates are preferable.

2) Aging Process It is not possible to separately prepare tabular grain nuclei during nucleation. Therefore, in the next ripening process, Ostwald ripening causes the tabular grains to grow and the other grains to disappear. The aging temperature is 40 ° C or higher, preferably 45 to 90 ° C, more preferably 50 to 80 ° C. In the present invention, it is preferable that the silver halide solvent is not allowed to substantially coexist even during ripening. Here, “substantially” complies with the above rules. PH during aging is 1 to 12, preferably 1.5 to
8, more preferably 1.7 to 6.

As the dispersion medium for nucleation, ripening and growth, a conventionally known dispersion medium for silver halide emulsions can be used, but the methionine content is particularly preferably 0-5.
0 μmol / g, more preferably 0 to 30 μmol / g gelatin can be preferably used. When the gelatin is used during ripening and growth, thinner tabular grains having a uniform diameter size distribution are formed, which is preferable. Also, Japanese Examined Patent Publication No. 52-16365, Journal of the Photographic Society of Japan, 29 volumes (1), 17, 22 (1966), 30 volumes (1),
10, 19 (1967), 30 volumes (2), 17 (1)
967), 33 (3), 24 (1967). Further, the crystal habit controlling agent described in European Patent 0534395A1 can be used in combination. The dispersion medium concentration is 0.1 to
10 wt% is preferable, and the control agent is preferably 10 ^-1 to
10 ⁻⁶ mol / L, more preferably 10 ⁻² to 10 ⁻⁵ mol / L
Can be used for L. These can be added at any time from before nucleation to the end of growth. It can be added in the form of additional addition to the existing dispersion medium, or can be added after removing the existing dispersion medium by centrifugation or the like.

3) Growth Process After the tabular grain ratio is increased by aging, a solute is added next to further grow the tabular grains. As the solute addition method, 1) a solution addition method (a method of adding a silver salt aqueous solution and a halide salt aqueous solution), 2) a fine grain emulsion addition method of previously forming fine silver halide grains and adding the fine grains,
3) A method of using both in combination. In order to preferentially grow the tabular grains in the edge direction, it is necessary to grow the tabular grains at a low supersaturation concentration within a range that does not undergo Ostwald ripening. That is, it is necessary to control the concentration at a low supersaturation level with high accuracy. 2)
The method (1) is more preferable because it enables this.

In the fine grain emulsion addition method, the diameter is 0.15 μm or less, preferably 0.1 μm or less, more preferably 0.1 μm or less.
A silver halide fine grain emulsion having a grain size of 06 μm or less is added, and tabular grains are grown by Ostwald ripening. The fine grain emulsion can be added continuously or intermittently. The fine grain emulsion can be continuously prepared by supplying an aqueous solution of silver salt and an aqueous solution of halide salt in a mixer provided in the vicinity of the reaction vessel, and can be continuously added to the reaction vessel immediately or in advance in another vessel. It is also possible to add it continuously or intermittently after it is prepared in a batch manner.
It is preferable that the fine particles are substantially free of twin grains. The term “substantially free of” means that the twin grain number ratio is 5% or less, preferably 1% or less, more preferably 0.5% or less.

The halogen composition of the fine grains may be silver chloride, silver bromide, silver iodide, or a mixed crystal of two or more thereof. The solution conditions during grain growth are the same as the above-mentioned aging conditions. This is because both are steps in which tabular grains are grown by Ostwald ripening and other fine particles are eliminated, and they are mechanically the same. For details of the method of adding a fine grain emulsion, see Japanese Patent Application Nos. 2-142635 and 4-4.
-77261 and JP-A-1-183417 can be referred to. In order to form fine particles having substantially no twin planes, the excess halogen ion concentration or the excess silver ion concentration is preferably 10 ^-2 mol / liter or less, and the silver salt aqueous solution and the halide salt aqueous solution are simultaneously mixed and added. It may be added by a method.

The fine particle formation temperature is preferably 50 ° C. or lower,
5-40 degreeC is more preferable, and 10-35 degreeC is still more preferable. The dispersion medium preferably has a molecular weight of 2000 to 6 × 10.
⁴ , more preferably 5000-4 × 10 ⁴ low molecular weight gelatin, preferably 30% by weight or more, more preferably 6
Gelatin occupying 0% by weight or more, and more preferably 80% by weight or more is preferable. The dispersion medium concentration is preferably 0.02% by weight or more, more preferably 0.1 to 5% by weight.

Dislocation lines can be introduced into the grains during the grain formation by the halogen composition gap method, the halogen conversion method, the epitaxial growth method and a combination thereof. The pressure fog characteristics and reciprocity law characteristics and the color sensitization characteristics are further improved, which is preferable. Regarding this, JP-A-63-2
20238, 64-26839, JP-A-2-1276
35, ibid 3-189642, ibid 3-175440, ibid 2
-123346, European Patent 0460656A1 Journal
of Imaging Science, 32 volumes, 160-177 (19
88) can be referred to.

The obtained particles may be used as host particles to form epitaxial particles for use. Further, particles having dislocation lines inside may be formed using the particles as a core.
In addition, using the grains as a substrate, a silver halide layer having a halogen composition different from that of the substrate is laminated,
It is also possible to make particles of various known particle structures.

Further, a shallow inner latent emulsion may be formed and used by using the tabular grains as a core. It is also possible to form core / shell type particles. Regarding this, JP-A-59-
133542, 63-151618, U.S. Pat. Nos. 3,206,313, 3,317,322, 3,761,276, 4,269,927, 3,367,778. Can be referred to.

As described above, the most important parameter for finally obtaining a silver halide grain having a high aspect ratio is pAg during ripening and growth.

On the surface of the tabular grains having a high silver chloride content, the principal plane of which is the (100) plane, of the present invention, a silver salt which is less soluble than silver chloride is preferably present. Examples of silver salts that are less soluble than silver chloride include silver bromide, silver iodide, silver iodobromide, silver thiocyanate, silver selenocyanate, and mixed crystals thereof. It is preferably silver halide.
The amount of the silver salt, which is less soluble than silver chloride, is 20 mol% or less, preferably 10 mol% or less, based on the whole grains.
More preferably 5 mol% or less, 0.001 mol%
That is all.

As the method of causing the silver salt, which is less soluble than silver chloride, to be present on the surface of the tabular grains, a method of adding a halide salt aqueous solution and a silver salt aqueous solution having a corresponding composition by a double jet method, a fine grain emulsion addition method, and A method of using a sustained release agent of bromide ion or iodine ion can be mentioned. In the method in which the water-soluble halide salt and the water-soluble silver salt are added by a double jet, the halogen ions are added in a free state even if the halide salt aqueous solution is diluted and added. There are limits to trying to reduce locality. This is especially difficult for tabular grains.
On the other hand, the method of adding a fine grain emulsion or the method of using a sustained-release agent is a preferable method for forming a salt, which is less soluble than silver chloride, uniformly on the surface of the grains.

The average spherical phase equivalent diameter of the fine particles in the fine grain emulsion addition method is preferably 0.1 μm or less, more preferably 0.06 μm or less. The fine particles are continuously prepared by supplying an aqueous solution of a silver salt and an aqueous solution of a salt capable of forming a silver salt having a solubility lower than that of silver chloride in a mixer provided in the vicinity of the reaction vessel, and immediately adding to the reaction vessel. Alternatively, it can be added after it is prepared in a batch manner in advance in another container. The method using a sustained-release agent is described in JP-B-1-28594.
2. Japanese Patent Application No. 5-58039 and the like.

Gelatin is advantageously used as a protective colloid used in the preparation of the emulsion of the present invention and as a binder for other hydrophilic colloid layers, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives;
Various synthetic hydrophilic polymers such as polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, polyvinyl pyrazole, single or copolymers. A substance can be used.

As gelatin, lime-processed gelatin, acid-processed gelatin and Bull. Soc. Sci. Photo. Japan.
No. 16. The enzyme-treated gelatin as described in P30 (1966) may be used, and a hydrolyzed product or an enzymatically decomposed product of gelatin may also be used.

The emulsion of the present invention is preferably washed with water for desalting and dispersed in a newly prepared protective colloid. The temperature for washing with water can be selected according to the purpose, but it is preferably selected within the range of 5 ° C to 50 ° C. The pH at the time of washing with water can also be selected according to the purpose, but it is preferably selected between 2 and 10. More preferably, it is in the range of 3-8. The pAg at the time of washing with water can also be selected according to the purpose, but it is preferably selected between 5 and 10. As a method of washing with water, a noodle washing method, a dialysis method using a semipermeable membrane,
It can be selected and used from a centrifugal separation method, a coagulation sedimentation method, and an ion exchange method. In the case of the coagulation sedimentation method, it can be selected from a method using a sulfate, a method using an organic solvent, a method using a water-soluble polymer, a method using a gelatin derivative and the like.

During preparation of the emulsion of the present invention, for example, during grain formation,
In the desalting step, during chemical sensitization, it is preferable to allow a salt of a metal ion to exist before coating, depending on the purpose. When the grains are doped, they are preferably added at the time of grain formation, when the grains are modified, or when used as a chemical sensitizer, after grain formation and before the end of chemical sensitization. For example, Mg, Ca, Sr, B
a, Al, Sc, Y, La, Cr, Mn, Fe, Co,
Ni, Cu, Zn, Ga, Ru, Rh, Pd, Re, O
s, Ir, Pt, Au, Cd, Hg, Tl, In, S
Metals such as n, Pb and Bi can be used. These metals can be added in the form of salts such as ammonium salts, acetates, nitrates, sulfates, phosphates, hydroxides or hexacoordinated complex salts and tetracoordinated complex salts which can be dissolved at the time of grain formation. For example, CdBr ₂ , CdCl ₂ , Cd
(NO ₃ ) ₂ , Pb (NO ₃ ) ₂ , Pb (CH ₃ CO
O) ₂ , K ₃ [Fe (CN) ₆ ], (NH ₄ ) ₄ [Fe
(CN) ₆ ], K ₃ IrCl ₆ , (NH ₄ ) ₃ RhCl
₆ , a metal compound such as K ₄ Ru (CN) ₆ . As a ligand of a coordination compound, halo, aco, cyano,
It can be selected from cyanate, thiocyanate, nitrosyl, thionitrosyl, oxo and carbonyl. Although these may use only one type of metal compound, 2
They may be used alone or in combination of three or more.

The metal compound is water or methanol, aceto
It is preferable to add it after dissolving it in a suitable organic solvent such as
Good Aqueous hydrogen halide solution to stabilize the solution
(Eg HCl, HBr) or halogenated alkali
(Eg KCl, NaCl, KBr, NaBr)
A method of adding can be used. If necessary, acid
・ Alkali may be added. Metal compounds form particles
Even if added to the previous reaction vessel, it must be added in the middle of particle formation
You can also In addition, a water-soluble silver salt (for example, AgNO ₃)Ah
Or an alkali halide aqueous solution (for example, NaCl,
KBr, KI) and continuously during the formation of silver halide grains.
Can also be added. Furthermore, water-soluble silver salt, halogen
Prepare a solution independent of alkali chloride and
You may add continuously in time. Further various addition methods
It is also preferable to combine

The method of adding a chalcogenide compound as described in US Pat. No. 3,772,031 during emulsion preparation may be useful in some cases. In addition to S, Se, and Te, cyanates, thiocyanates, selenocyanates, carbonates,
Phosphate and acetate may be present.

In the base grain of the present invention, at least one of sulfur sensitization, selenium sensitization, tellurium sensitization, gold sensitization, palladium sensitization or noble metal sensitization, and reduction sensitization is used in any of the steps for producing a silver halide emulsion. Can be applied in the process of. It is preferable to combine two or more sensitizing methods. Various types of emulsions can be prepared depending on which step is chemically sensitized. There are a type in which chemically sensitized nuclei are embedded inside a grain, a type in which a chemical sensitized nucleus is embedded at a shallow position from the grain surface, and a type in which a chemically sensitized nucleus is formed on the surface. In the emulsion of the present invention, the location of the chemically sensitized nucleus can be selected according to the purpose, but it is generally preferable that at least one type of chemically sensitized nucleus is formed near the surface.

One of the chemical sensitizations which can be preferably carried out in the present invention is chalcogenide sensitization and noble metal sensitization, alone or in combination, by TH James, The Photographic Process, 4th Edition, Macmillan Company. Published, 197
7 years, (THJames, The Theory of the Photographic
Process, 4th ed, Macmillan, 1977) 67-76, using active gelatin, and Research Disclosure, 120 volumes,
April 1974, 12008; Research Disclosure, 34, June 1975, 13452, U.S. Pat. Nos. 2,642,361 and 3,297,446.
No. 3,773,031, No. 3,857,71
No. 1, No. 3,901,714, No. 4,226,0
18 and 3,904,415 and pAg as described in British Patent 1,315,755.
It can be sulfur, selenium, tellurium, gold, platinum, palladium or combinations of these sensitizers at 5-10, pH 5-8 and temperature 30-80 ° C. In the noble metal sensitization, for example, a noble metal salt of gold, platinum or palladium can be used, and among them, gold sensitization, palladium sensitization and a combination of both are preferable. In the case of gold sensitization, known compounds such as chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide and gold selenide can be used. The palladium compound means a divalent or tetravalent palladium salt. Preferred palladium compounds are P ₂ PdX ₆ or R ₂ PdX
Represented by ₄ . 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, for example, K ₂ PdCl ₄ ,
(NH ₄ ) ₂ PdCl ₆ , Na ₂ PdCl ₄ , (N
H ₄ ) ₂ PdCl ₄ , Li ₂ PdCl ₄ , Na ₂ PdC
₁₆ or K ₂ PdBr ₄ is preferred. The gold compound and the palladium compound are preferably used in combination with thiocyanate or selenocyanate.

As sulfur sensitizers, hypo, thiourea compounds, rhodanine compounds and US Pat. No. 3,857,
711, 4,226,018 and 4,0.
The sulfur-containing compounds described in No. 54,457 can be used. It is also possible to carry out chemical sensitization in the presence of a so-called chemical sensitizer. Useful chemical sensitization aids include compounds known to suppress fog and increase sensitivity during the chemical sensitization process, such as azaindene, azapyridazine and azapyrimidine. Examples of chemical sensitization aid modifiers include U.S. Pat. Nos. 2,131,038, 3,411,914, 3,554,757, JP-A-58-126526 and the above-mentioned Daffin. "Photographic Emulsion Chemistry", pages 138-143.

The emulsion of the present invention is preferably combined with gold sensitization. The amount of the gold sensitizer is preferably 1 × 10 ⁻⁴ to 1 × 10 ⁻⁷ mol, and more preferably 1 × 10 ^{−5 to} 5 × 10 ⁻⁷ mol, per mol of silver halide. The preferable range of the palladium compound is 1 × 10 ⁻³ to 5 × 10 ⁻⁷ . The preferred range of the thiocyan compound or selenocyan compound is 5 × 10 ^-2 to 1 × 10 ^-6 . The preferred amount of sulfur sensitizer used for the silver halide grains of the present invention is from 1 × 10 ⁻⁴ to 1 × 10 ⁴ per mol of silver halide.
^-7 mol, more preferably 1 × 10 ^{-5 to} 5 × 1
It is ^0-7 mol.

Selenium sensitization is a preferred sensitizing method for the emulsion of the present invention. In the selenium sensitization, a known unstable selenium compound is used, and specifically, for example, colloidal metal selenium, selenoureas (eg, N, N-dimethylselenourea, N, N-diethylselenourea, etc.),
Selenium compounds such as selenoketones and selenoamides can be used. In some cases, selenium sensitization is preferably used in combination with sulfur sensitization, precious metal sensitization, or both. The silver halide emulsion of the present invention is preferably subjected to reduction sensitization during grain formation, after grain formation and before or during chemical sensitization, or after chemical sensitization.

Here, the reduction sensitization is a method of adding a reduction sensitizer to a silver halide emulsion, pAg1 called silver ripening.
No. 7, a method of growing or aging in a low pAg atmosphere, or a method of growing or aging in a high pH atmosphere of pH 8 to 11 called high pH 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 the reduction sensitizer, for example, stannous salt, ascorbic acid and its derivatives, amines and polyamines, hydrazine derivatives, formamidinesulfinic acid, silane compounds,
Borane compounds are known. For the reduction sensitization of the present invention, these known reduction sensitizers can be selected and used.
It is also possible to use two or more compounds in combination. As reduction sensitizers, stannous chloride, thiourea dioxide, dimethylamine borane, ascorbic acid and its derivatives are preferred compounds. Since the addition amount of the reduction sensitizer depends on the emulsion production conditions, it is necessary to select the addition amount, but the range of 10 ^-7 to 10 ^-3 mol is suitable per mol of silver halide.

The reduction sensitizer is dissolved in water or an organic solvent such as alcohols, glycols, ketones, esters and amides and added during grain growth. It may be added to the reaction vessel in advance, but it is preferable to add it at an appropriate time during grain growth. Further, a reduction sensitizer may be added in advance to the water solubility of the water-soluble silver salt or the water-soluble alkali halide, and the silver halide grains may be precipitated using these aqueous solutions. Further, it is also a preferable method to add the solution of the reduction sensitizer in several times as the grains grow, or to continuously add the solution for a long time.

It is preferable to use an oxidizing agent for silver during the process of producing the emulsion of the present invention. What is an oxidizing agent for silver?
It refers to a compound that acts on metallic silver to convert it into silver ions. In particular, a compound capable of converting extremely fine silver grains, which are a by-product in the process of forming silver halide grains and the process of chemical sensitization, into silver ions is effective. The silver ions generated here are, for example, silver halide, silver sulfide,
May form a sparingly soluble silver salt such as silver selenide,
Further, a silver salt which is easily soluble in water such as silver nitrate may be formed.
The oxidizing agent for silver may be an inorganic substance or an organic substance. Examples of the inorganic oxidant include ozone, hydrogen peroxide and its adducts (for example, NaBO ₂ .H ₂
O ₂ · 3H ₂ O, 2NaCO ₃ · 3H ₂ O ₂ , Na ₄ P
₂ O ₇・ 2H ₂ O ₂ , 2Na ₂ SO ₄・ H ₂ O ₂・ 2H
₂ OH), peroxy acid salts (eg K ₂ S ₂ O ₈ , K
₂ C ₂ O ₆ , K ₂ P ₂ O ₈ ) and peroxy complex compounds (for example, K ₂ [Ti (O ₂ ) C ₂ O ₄ ] .3H ₂ O,
4K ₂ SO ₄ · Ti (O ₂ ) OH · SO ₄ · 2H ₂ O,
_{Na 3 [VO (O 2)} (C 2 H 4) 2 · 6H 2 O], permanganate (e.g., KMnO _4), oxygen acid salts, such as chromates (e.g., K ₂ Cr ₂ O ₇₎ There are halogen elements such as iodine and bromine, perhalogenates (eg potassium periodate), salts of high-valent metal (eg potassium hexacyanoferrate) and thiosulfonates.

As the organic oxidant, for example, p
-Quinones such as quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogen (for example, N-bromosuccinimide, chloramine T, chloramine B). Preferred oxidants of the present invention are ozone, hydrogen peroxide and its adducts, halogen elements, inorganic oxidizers of thiosulfonates and organic oxidants of quinones. It is a preferable embodiment to use the reduction sensitization and the oxidizing agent for silver in combination. It can be selected from the method of using an oxidant and then the reduction sensitization, the reverse method thereof, or the method of coexisting both. These methods can be selectively used in the grain forming step and the chemical sensitization step.

The photographic emulsion used in the present invention may contain 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. . That is, thiazoles, for example, benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, Aminotriazoles, benzotriazoles,
Nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadrinethione; azaindenes, for example triazaindenes, tetra Azaindenes (especially 4-hydroxy substituted (1,
Many compounds known as antifoggants or stabilizers such as 3,3a, 7) chitraazaindenes), pentaazaindenes can be added. For example, U.S. Pat. Nos. 3,954,474 and 3,982,94
No. 7 and Japanese Patent Publication No. 52-28660 can be used. JP-A-63-63 is one of the preferred compounds.
There are compounds described in No. 212932. Antifoggants and stabilizers are used at various times before particle formation, during particle formation, after particle formation, during the water washing step, during dispersion after water washing, before chemical sensitization, during chemical sensitization, after chemical sensitization, and before coating. It can be added depending on the purpose. In addition to adding the effect of preventing fog and stabilizing during the preparation of the emulsion, the crystal wall of the grain is controlled, the grain size is reduced, the solubility of the grain is reduced, and the chemical sensitization is controlled. It can be used for various purposes such as controlling the arrangement of dyes.

As the spectral sensitizing dye to be adsorbed on the base grains of the present invention, there is a methine dye, and therefore the photographic emulsion finally obtained is also spectrally sensitized with methine dyes and the like. It is preferable to exhibit. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. 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, for example, pyrroline nucleus, oxazoline nucleus, thiozoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus,
Imidazole nuclei, tetrazole nuclei, pyridine nuclei; nuclei in which alicyclic hydrocarbon rings are fused to these nuclei; and nuclei in which aromatic hydrocarbon rings are fused to these nuclei, that is, for example, indolenine nuclei, benzindolenine Nucleus, indole nucleus, benzoxadol nucleus, naphthoxazole nucleus,
The benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus and quinoline nucleus 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, for example, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, 2
5-6 membered heterocyclic nuclei can be applied, such as -thioxazolidine-2,4-dione nuclei, thiazolidine-2,4-dione nuclei, rhodanin nuclei and thiobarbituric acid nuclei.

These sensitizing dyes may be used alone or in combination thereof, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization. Typical examples thereof are US Pat. Nos. 2,688,545 and 2,972.
7,229, 3,397,060, 3,5
No. 22,052, No. 3,527,641, No. 3,
617, 293, 3,628,964, 3,666,480, 3,672,898, 3,679,428, 3,703,377,
No. 3,769,301, No. 3,814,609
No. 3,837,862, No. 4,026,70
7, British Patent Nos. 1,344,281 and 1,50
No. 7,803, Japanese Patent Publication No. 43-4936, No. 53-12
No. 375, JP-A Nos. 52-110618 and 52-10.
No. 9925. Along with the sensitizing dye, a dye having no spectral sensitizing effect by itself or a substance which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion.

The preferred time for adding the spectral sensitizing dye of the present invention is after the base grains are formed and before the fine grains are added. Most commonly, it is carried out after the completion of chemical sensitization and before coating, but U.S. Pat. Nos. 3,628,969 and 4,
It is also possible to add spectral sensitization at the same time as the chemical sensitizer as described in JP-A No. 225,666 and to perform chemical sensitization at the same time as described in JP-A-58-113928. It can be carried out prior to the sensitization, or it can be added before the completion of silver halide grain precipitation to start the spectral sensitization. Furthermore, US Pat. No. 4,255,666
It is also possible to add these said compounds separately, as taught in US Pat. No. 6,096,097, ie to add some of these compounds prior to chemical sensitization and the rest after chemical sensitization. And at any time during the formation of silver halide grains, including the method disclosed in U.S. Pat. No. 4,183,756.

The addition amount is 4 × per mol of silver halide.
It can be used in an amount of 10 ⁻⁶ to 8 × 10 ⁻³ mol, but in the case of a more preferable silver halide grain size of 0.2 to 1.2 μm, about 5 × 10 ⁻⁵ to 2 × 10 ⁻³ mol is more effective. Is. When the emulsion obtained in the present invention is used as a light-sensitive material, various additives described above are used, but various additives other than the above can be used according to the purpose. These additives are described in more detail in Research Disclosure It
em 17643 (December 1978), Item
18716 (November 1979) and Item 3 of the same.
No. 08119 (December 1989), and the corresponding portions are summarized in Table 1 below.

[0065]

[Table 1]

The light-sensitive material of the present invention may have at least one silver halide emulsion layer of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer provided on a support. There is no particular limitation on the number and order of layers of the silver halide emulsion layer and the non-photosensitive layer. As a typical example, a silver halide photographic light-sensitive material having on a support at least one light-sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. And the photosensitive layer is blue light, green light,
And a unit light-sensitive layer having color sensitivity to red light. In a multilayer silver halide color photographic light-sensitive material, the unit light-sensitive layers are generally arranged in order from the support side to the red-color-sensitive layer and green. The color sensitive layer and the blue color sensitive layer are installed in this order. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers.

Non-photosensitive layers such as various intermediate layers may be provided between the above-described silver halide photosensitive layers and as the uppermost layer and the lowermost layer. For the intermediate layer, JP-A Nos. 61-43748, 59-113438, 59-113440 and 6-61 are used.
The couplers and DIR compounds as described in the specifications of 1-20037 and 61-20038 may be contained, and a color mixing inhibitor may be contained as is commonly used. A plurality of silver halide emulsion layers constituting each unit light-sensitive layer are composed of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer as described in West German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer structure can be preferably used. In general, it is preferable that the layers are arranged so that the photosensitivity is gradually lowered toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Further, as described in JP-A-57-112751, JP-A-62-200350, JP-A-62-206541, 62-206543, etc., a low-sensitivity emulsion layer on the side remote from the support,
A high sensitivity emulsion layer may be provided on the side closer to the support.

As a specific example, from the side farthest from the support,
Low sensitivity blue photosensitive layer (BL) / high sensitivity blue photosensitive layer (BH)
/ High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (G
L) / high-sensitivity red photosensitive layer (RH) / low-sensitivity red photosensitive layer (RL), or BH / BL / GL / GH / RH /
RL order or BH / BL / GH / GL / RL / RH
It can be installed in the order of. In addition, Japanese Examined Japanese Patent Publication Sho 55-34
As described in Japanese Patent No. 932, the blue-sensitive layer / GH / RH / GL / RL may be arranged in this order from the side farthest from the support. Also, JP-A-56-25738
No. 62-63936, the blue-sensitive layer / GL / RL from the side farthest from the support.
It can also be arranged in the order of / GH / RH.

As described in JP-B-49-15495, the upper layer is the silver halide emulsion layer having the highest photosensitivity, the middle layer is the silver halide emulsion layer having a lower photosensitivity, and the lower layer is the middle layer. Another example is an arrangement in which a silver halide emulsion layer having a lower photosensitivity is arranged and three layers having different sensitivities are sequentially lowered toward the support. Even when it is composed of three layers having different sensitivities, as described in JP-A-59-202464, a medium-sensitivity emulsion from the side remote from the support in the same color-sensitive layer. Layers / high-speed emulsion layers / low-speed emulsion layers may be arranged in this order.

In addition, the layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer. Also, 4
In the case of more than one layer, the arrangement may be changed as described above. As described above, various layer configurations and arrangements can be selected according to the purpose of each light-sensitive material. In the photographic light-sensitive material of the present invention, at least one silver halide emulsion layer provided on a support contains the silver halide emulsion of the present invention in an amount of 30% or more, preferably 50% or more, more preferably 70% or more. It is a silver halide photographic light-sensitive material containing.

About 3 silver halides other than the silver halide of the present invention contained in the photographic emulsion layer of the photographic light-sensitive material of the present invention.
Silver iodobromide, silver iodochloride, or silver iodochlorobromide containing 0 mol% or less of silver iodide is preferable. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide. However, it is preferable that the content of silver bromide contained in the entire light-sensitive material is low, and the content of silver iodide is also low. Silver halide grains other than the silver halide of the present invention in a photographic emulsion are those having regular crystals such as cubes, octahedra and tetradecahedrons, and irregular crystal forms such as spheres and plates. Those having crystal defects such as twin planes, or a composite form thereof.

The grain size of the silver halide other than the silver halide of the present invention may be fine grains of about 0.2 micron or less, or large grains having a projected area diameter of up to about 10 microns, and it may be a monodisperse emulsion or a monodisperse emulsion. It may be a dispersion emulsion. The silver halide emulsion used in the present invention is usually one that has been physically ripened, chemically ripened and spectrally sensitized. The methods of physical ripening, chemical ripening and spectral sensitization can be carried out in the same manner as in the above high silver chloride (100) tabular grains.

The above-mentioned various additives are used in the emulsion of the present invention, but various additives other than the above can be used depending on the purpose. These additives are described in more detail in Research Disclosure Item 1764
3 (December 1978), Item 18716 (1)
997) and Item 308119 (1)
(December 989), and the relevant parts are summarized in Table 1 below.

The light-sensitive material of the present invention comprises a photosensitive silver halide emulsion having a grain size, a grain size distribution, a halogen composition,
Two or more kinds of emulsions having at least one characteristic of grain shape and sensitivity can be mixed and used in the same layer.

The fogged silver halide grains described in US Pat. No. 4,082,553 and the fogged grains described in US Pat. No. 4,626,498 and JP-A-59-214852 are fogged. The prepared silver halide grains and colloidal silver can be preferably used in the photosensitive silver halide emulsion layer and / or the substantially non-photosensitive hydrophilic colloid layer.
The fogged silver halide grain inside or on the surface means a silver halide grain capable of developing uniformly (non-imagewise) regardless of the unexposed portion and exposed portion of the light-sensitive material. . A method for preparing a silver halide grain whose inside or surface is fogged is described in US Pat. No. 4,626,498 and JP-A-59-214852.

The silver halide forming the inner nucleus of a core / shell type silver halide grain having a fogged grain inside may have the same halogen composition or different halogen compositions. As the silver halide whose inside or surface is fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. The grain size of these fogged silver halide grains is not particularly limited, but the average grain size is 0.01 to 0.7.
The thickness is preferably 5 μm, particularly preferably 0.05 to 0.6 μm. Also,
The grain shape is not particularly limited, and may be regular grains or polydisperse emulsion, but monodisperse (at least 95% of the weight or the number of silver halide grains is within ± 40% of the average grain size). (Having a particle size of 1).

In the present invention, it is preferable to use a non-photosensitive fine grain silver halide. The non-photosensitive fine grain silver halide is a fine grain of silver halide which is not exposed to light during imagewise exposure for obtaining a dye image and is not substantially developed in the development process, and it is preferable that it is not fogged in advance. .

The fine grain silver halide has a silver chloride content of 0 to 100 mol%, and if necessary, silver bromide and / or
Alternatively, it may contain silver iodide. Preferably, it contains 0.5 to 10 mol% of silver bromide. Fine grain silver halide has an average grain size (average value of circle equivalent diameter of projected area)
Is preferably 0.01 to 0.5 μm, and 0.02 to 0.2
μm is more preferable. The fine grain silver halide can be prepared by a method similar to that for ordinary photosensitive silver halide. In this case, the surface of the silver halide grain does not need to be chemically sensitized nor spectral sensitization. However, prior to adding this to the coating liquid, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, mercapto-based compound or zinc compound in advance. Colloidal silver can be preferably contained in this fine grain silver halide grain-containing layer.

The coated silver amount of the light-sensitive material of the present invention is 8.0 g.
/ M ² or less is preferable, 6.0 g / m ² or less is more preferable, and 4.5 g / m ² or less is most preferable. Known photographic additives that can be used in the present invention are also the above three research items.
It is described in the disclosure, and the relevant portions are shown in Table 1 below. Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, US Pat.
It is preferable to add to the photographic material a compound which can be immobilized by reacting with formaldehyde described in 411,987 and 4,435,503.

The light-sensitive material of the present invention can be prepared by the method of US Pat.
0,454, 4,788,132, JP-A-62.
It is preferable to incorporate the mercapto compounds described in JP-A-18539 and JP-A-1-283551. A compound which, in the light-sensitive material of the present invention, releases a fog agent, a development accelerator, a silver halide solvent or a precursor thereof, which is described in JP-A No. 1-106052, irrespective of the amount of developed silver produced by the development processing. Is preferably contained. Dyes dispersed in the light-sensitive material of the present invention by the method described in International Publication WO88 / 04794 and Japanese Patent Publication No. 1-502912 or EP 317,308A, US Pat.
It is preferable to incorporate the dyes described in JP-A No. 20,555 and JP-A No. 1-259358.

Various color couplers can be used in the present invention, and specific examples thereof are described in Research Disclosure No. 17643, VII-CG, and No. 17643. 307105, VII-C to G. Examples of yellow couplers include US Pat. Nos. 3,933,501 and 4,022,62.
No. 0, No. 4,326,024, No. 4,401,7
No. 52, No. 4,248,961, Japanese Patent Publication No. 58-10
739, British Patent Nos. 1,425,020 and 1,
476,760, U.S. Pat. No. 3,973,968,
No. 4,314,023, No. 4,511,649
And those described in European Patent No. 249,473A and the like are preferable.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619 and 4,351,897 are preferred.
No., EP 73,636, US Pat. No. 3,06
No. 1,432, No. 3,725,067, Research
Disclosure No. 24220 (June 1984)
Mon.), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, 61-72238 and 60.
-35730, 55-118034, 60-1
Those described in US Pat. No. 8,5951, US Pat. Nos. 4,500,630, 4,540,654, 4,556,630, International Publication WO88 / 04795 and the like are particularly preferable.

Examples of cyan couplers include phenol-type and naphthol-type couplers, and US Pat.
No. 52,212, No. 4,146,396, No. 4,
No. 228,233, No. 4,296,200, No. 2,369,929, No. 2,801,171, No. 2,772,162, No. 2,895,826,
No. 3,772,002, No. 3,758,308
No. 4,433,011, No. 4,327,17
No. 3, West German Patent Publication No. 3,329,729, European Patent Nos. 121,365A, No. 249,453A, U.S. Patent Nos. 3,446,622 and 4,333,999.
Issue No. 4,775,616, No. 4,451,55
No. 9, No. 4,427, 767, No. 4, 690, 8
No. 89, No. 4,254,212, No. 4,296,
Those described in JP-A No. 199 and JP-A No. 61-42658 are preferable.

Typical examples of polymerized dye-forming couplers are shown in US Pat. Nos. 3,451,820 and 4,084.
No. 0,211, No. 4,367,282, No. 4,4
09,320, 4,576,910, British Patent 2,102,137, European Patent 341,188A and the like. Examples of the coupler in which the color forming dye has an appropriate diffusibility include US Pat. No. 4,366,237,
British Patent No. 2,125,570, European Patent No. 96,5
70 and West German Patent (Publication) No. 3,234,533 are preferable.

Colored couplers for correcting unwanted absorption of color forming dyes are available from Research Disclosure N.
o. 17643, Item VII-G, ibid. Of 307105
Section VII-G, U.S. Pat. No. 4,163,670, Japanese Patent Publication No. 57-39413, U.S. Pat. No. 4,004,929.
No. 4,138,258, British Patent No. 1,14.
Those described in 6,368 are preferable. Further, a coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in US Pat. No. 4,774,181 and a reaction with a developing agent described in US Pat. No. 4,777,120. It is also preferable to use a coupler having as a leaving group a dye precursor group capable of forming a dye.

Compounds releasing a photographically useful residue upon coupling are also preferably used in the present invention.
DIR couplers that release development inhibitors are described in RD.
17643, Item VII-F and No. 307105, V
Patents described in the section II-F, JP-A-57-151944
No. 57-154234, No. 60-184248.
Nos. 63-37346, 63-37350, and U.S. Pat. Nos. 4,248,962 and 4,782,012 are preferable.

As a coupler capable of releasing a nucleating agent or a development accelerator imagewise during development, British Patent No. 2,092
7,140, 2,131,188, JP-A-59
Those described in Nos. 157638 and 59-170840 are preferable. Further, JP-A-60-107029, JP-A-60-252340, JP-A-1-44940 and JP-A-1-4940.
Compounds releasing a fog agent, a development accelerator, a silver halide solvent and the like by an oxidation-reduction reaction with an oxidized product of a developing agent described in JP-A-45687 are also preferable.

Other compounds that can be used in the light-sensitive material of the present invention include US Pat. No. 4,130,427.
Competitive couplers described in U.S. Pat. No. 4,283,4
No. 72, No. 4,338,393, No. 4,310,
No. 618 and the like, multiequivalent couplers, JP-A-60-18.
5950, DI described in JP-A-62-24252, etc.
R redox compound-releasing coupler, DIR coupler-releasing coupler, DIR coupler-releasing redox compound or DIR redox-releasing redox compound, coupler releasing a dye that recolors after separation described in European Patent Nos. R.K. D. N
o. 11449, 24241, JP-A-61-2012
47, etc., bleaching accelerator releasing couplers, US Pat. No. 4,555,477, etc., ligand releasing couplers, JP-A-63-75747, leuco dye releasing couplers, US Pat. , 774,181, and the like, which release a fluorescent dye.

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. 2,322,222.
No. 027 and the like.

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 (eg 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), phosphoric acid or phosphone Acid esters (eg triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2)
-Ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenylphosphonate), benzoic acid esters (e.g. 2-ethylhexylbenzoate), dodecylbenzoate, 2
-Ethylhexyl-p-hydroxybenzoate), amides (e.g. N, N-diethyldodecane amide, N,
N-diethyllaurylamide, N-tetradecylpyrrolidone), alcohols or phenols (eg isostearyl alcohol, 2,4-di-tert-amylphenol), aliphatic carboxylic acid esters (eg bis (2-ethylhexyl)) Sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate), aniline derivatives (eg N, N-dibutyl-2-butoxy-5-te).
rt-octylaniline), hydrocarbons (eg paraffin, dodecylbenzene, diisopropylnaphthalene)
And so on. The auxiliary solvent has a boiling point of about 3
An organic solvent having a temperature of 0 ° C. or higher, preferably 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, dimethylformamide and the like. To be

The steps and effects of the latex dispersion method and specific examples of latex for impregnation are described in US Pat. No. 4,199,3.
63, West German Patent Application (OLS) No. 2,541,274
And No. 2,541,230. The photographic light-sensitive material of the present invention contains phenethyl alcohol, JP-A-63-257747 and JP-A-62-272224.
No. 8, and 1,2-described in JP-A No. 1-80941.
Benzisothiazolin-3-one, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,
5-dimethylphenol, 2-phenoxyethanol,
It is preferable to add various antiseptics or antifungal agents such as 2- (4-thiazolyl) benzimidazole.

The present invention can be applied to various photographic light-sensitive materials. Typical examples are color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers.
Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D. No. 17643, page 28, ibid. No. 18716, page 647, right column to page 648, left column, and ibid. 307
105, p. 879.

In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, more preferably 23 μm or less, and 18 μm or less.
m or less is more preferable, and 16 μm or less is particularly preferable.
The film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness means a film thickness measured under a humidity condition of 25 ° C. and a relative humidity of 55% (2 days), and the film swelling rate T
_1/2 can be measured according to a method known in the art. For example, A. Green
) Et al., Photographic Science and Engineering (Photogr.Sci.Eng.), Volume 19, 2
No., pages 124 to 129 can be measured by using a swellometer (swelling meter) of the type described, and T _1/2 is the maximum swell reached when the color developing solution is processed at 38 ° C. for 3 minutes and 15 seconds. 90% of the film thickness is defined as the saturated film thickness, and is defined as the time required to reach 1/2 of the saturated film thickness.

The film swelling speed T _1/2 can be adjusted by giving a film hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling rate is preferably 150 to 400%. The swelling rate is calculated from the maximum swollen film thickness under the above-mentioned conditions by the formula:
It can be calculated according to (maximum swollen film thickness-film thickness) / film thickness.
The photosensitive material of the present invention is preferably provided with a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer. This back layer preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, surface active agent and the like. The swelling ratio of this back layer is 150 to 500%
Is preferred.

The light-sensitive material according to the present invention has the RD.
No. 7643, pages 28 to 29, No. 18716, 651, left column to right column,
And the conventional method described in No. 307105, pp. 880-881. The color developing solution used for the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. As the color developing agent, aminophenol compounds are also useful, but p-phenylenediamine compounds are preferably used, and a typical example thereof is 3-
Methyl-4-amino-N, N diethylaniline, 3-methyl-4-
Amino-N-ethyl-N-β-hydroxyethylaniline,
3-Methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl
-β-methoxyethylaniline, 4-amino-3-methyl-N
-Methyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N- ( 2-hydroxypropyl) aniline, 4-amino-3-ethyl-N-ethyl
-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-propyl-N- (3-hydroxypropyl) aniline, 4-amino-3-propyl-N-methyl-N- (3- Hydroxypropyl) aniline, 4-amino-3-methyl-N-methyl-N
-(4-hydroxybutyl) aniline, 4-amino-3-methyl
-N-ethyl-N- (4-hydroxybutyl) aniline, 4-amino-3-methyl-N-propyl-N- (4-hydroxybutyl) aniline, 4-amino-3-ethyl-N-ethyl-N -(3-Hydroxy-2-methylpropyl) aniline, 4-amino-3-methyl
-N, N-bis (4-hydroxybutyl) aniline, 4-amino
-3-Methyl-N, N-bis (5-hydroxypentyl) aniline, 4-amino-3-methyl-N- (5-hydroxypentyl) -N
-(4-hydroxybutyl) aniline, 4-amino-3-methoxy-N-ethyl-N- (4-hydroxybutyl) aniline, 4-amino-3-ethoxy-N, N-bis (5-hydroxypentyl)
Aniline, 4-amino-3-propyl-N- (4-hydroxybutyl) aniline, and their sulfates, hydrochlorides or p-
Examples thereof include toluene sulfonate. Among these, especially 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 4-amino-3-methyl-N-ethyl
-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N- (4-hydroxybutyl) aniline, and their hydrochlorides, p-toluenesulfonates or sulfates are preferred. . Two or more of these compounds can be used in combination depending on the purpose.

The amount of the aromatic primary amine developing agent used is preferably 0.0002 mol to 0.2 mol, and more preferably 0.001 mol to 1 mol, per liter of the color developing solution.
It is 0.1 mol.

The color developer contains a pH buffering agent such as an alkali metal carbonate, borate or phosphate 5-sulfosalicylate, a chloride salt, a bromide salt, an iodide salt, a benzimidazole compound, and a benzoic acid salt. It generally contains a development inhibitor such as a thiazole or a mercapto compound or an antifoggant. In addition, hydroxylamine, diethylhydroxylamine, etc. may be used, if necessary.
Hydroxylamines represented by the general formula (I) of No. 144446, sulfites, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides,
Various preservatives such as triethanolamine and catechol sulfonic acids, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye forming couplers and competitive couplers. , Various chelating agents represented by auxiliary developing agents such as 1-phenyl-3-pyrazolidone, tackifiers, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids, for example, ethylenediamine Tetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid,
Representative examples thereof include nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof. .

Of the above, substituted hydroxylamines are most preferable as the preservative, and those having an alkyl group substituted with a water-soluble group such as a sulfo group, a carboxy group or a hydroxyl group as a substituent are preferable among them. The most preferable example is N, N-bis (2-sulfoethyl) hydroxylamine and its alkali metal salt. Further, a compound having biodegradability is preferable as the chelating agent. Examples of this are Japanese Patent Laid-Open Nos. 63-146998 and 63-6398.
Chelating agents described in 199295, JP-A-63-267750, JP-A-63-267751, JP-A-2-229146, JP-A-3-186841, German Patent 3739610, European Patent 468325 and the like. be able to. It is preferable that the processing solution in the color developing solution replenishing tank or the processing tank is shielded with a liquid agent such as a high-boiling point organic solvent to reduce the contact area with air. Liquid paraffin is most preferable as the liquid shield agent. It is particularly preferable to use it as a replenisher.

The processing temperature of the color developing solution in the present invention is 20 to 55 ° C, preferably 30 to 55 ° C. The processing time is 20 seconds to 5 minutes, preferably 3 for the light-sensitive material for photography.
It is 0 seconds to 3 minutes and 20 seconds. It is more preferably 40 seconds to 2 minutes and 30 seconds, and for printing materials, 10 seconds to 1 minute 20 seconds, preferably 10 seconds to 60 seconds, and more preferably 10 seconds to 40 seconds.

When the reversal process is carried out, black and white development is usually carried out before color development. In this black-and-white developer, 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 are used alone. Alternatively, they can be used in combination. The color developing solution and the black and white developing solution generally have a pH of 9 to 12. The replenishment amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per 1 m 2 of the light-sensitive material. By reducing the chloride or bromide ion concentration in the replenishing solution, It can be less than 500 ml. When the replenishment amount is reduced, it is preferable to prevent the liquid evaporation and air oxidation by reducing the contact area of the treatment tank with the air. The contact area between the photographic processing liquid and air in the processing tank can be represented by the aperture ratio defined below. That is, aperture ratio = [contact area between treatment liquid and air (cm ² )] ÷ [volume of treatment liquid (cm ³ )] The above aperture ratio is preferably 0.1 or less, and more preferably 0.001 to 0.05. Is. As a method for reducing the aperture ratio in this way, in addition to providing a cover such as a floating lid on the surface of the photographic processing liquid in the processing tank, a method using a movable lid described in JP-A-1-82033 is disclosed. The slit development processing method described in 63-216050 can be mentioned. Reducing the aperture ratio is not limited to both the color development and black and white development steps, but also the subsequent steps such as bleaching, bleach-fixing,
It is preferably applied in all steps such as fixing, washing with water, and stabilization. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution.

The photographic emulsion layer 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, treatment with two continuous bleach-fixing baths, fixing treatment before the bleach-fixing treatment, or bleaching treatment after the bleach-fixing treatment can be optionally carried out. As the bleaching agent, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds and the like are used. As a typical bleaching agent, an organic complex salt of iron (III),
For example, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, glycol etherdiaminetetraacetic acid, JP-A-4
No. 121739, a bleaching agent including a 1,3-propylenediaminetetraacetic acid iron complex salt in the lower right column of the fourth page to the upper left column of the fourth page, and a carbamoyl-based bleaching agent described in JP-A-4-73647. Bleaching agents, bleaching agents having a heterocycle described in JP-A-4-174432, bleaching agents described in European Patent Publication No. 520457, including N- (2-carboxyphenyl) iminodiacetic acid ferric complex salts. Japanese Patent Application No. 3-252775 including ethylenediamine-N-2-carboxyphenyl-N, N ', N'-ferric acetic acid
Bleaching agent, bleaching agent described in EP-A-501479, bleaching agent described in JP-A-4-127145,
The ferric aminopolycarboxylic acid salts or salts thereof described on page (11) of JP-A-3-144446 are preferably used. The organic aminocarboxylic acid iron (III) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution.
The pH of the bleaching solution or bleach-fixing solution using these organic aminocarboxylic acid iron (III) complex salts is usually 4.0 to 8, but it is also possible to process at a lower pH for speeding up the processing.

These bleaching treatments are preferably carried out immediately after color development, but in the case of reversal treatments, they are generally carried out via an adjusting bath (which may be a bleaching promoting bath). These adjusting baths may contain an image stabilizer described later. In the present invention, in addition to the bleaching agent, the desilvering bath is described in JP-A-3-144446 (1).
2) Rehalogenating agents, pH buffers and known additives described on page, aminopolycarboxylic acids, organic phosphonic acids and the like can be used. Further, in the present invention, various bleaching accelerators can be added to the bleaching solution or its prebath. Examples of such bleaching accelerators include, for example, US Pat. No. 3,893,858 and German Patents 1, 2
90,821, British Patent No. 1,138,842.
Specification, JP-A-53-95630, research
Compounds having a mercapto group or a disulfide group described in Disclosure No. 17129 (July 1978 issue), thiazolidine derivatives described in JP-A No. 50-140129, described in US Pat. No. 3,706,561. Thiourea derivative of JP-A-58-16235
Iodide described in German Patent 2,748,43
The polyethylene oxides described in No. 0 specification, the polyamine compounds described in JP-B-45-8836, and the like can be used. Further, the compounds described in US Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photography. Particularly preferred are mercapto compounds as described in British Patent 1,138,842 and JP-A-2-190856.

In addition to the above compounds, the bleaching solution and the bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach stain. A particularly preferred organic acid has an acid dissociation constant (p
Ka) is 2 to 5.5, and dibasic acid is particularly preferable. The organic acid is specifically acetic acid as a monobasic acid,
Propionic acid, hydroxyacetic acid and the like are preferable, and more preferable dibasic acids include succinic acid, glutaric acid, maleic acid, fumaric acid, malonic acid, adipic acid and the like. Most preferred are succinic acid, glutaric acid and maleic acid.

The total time of the desilvering process is preferably as short as possible in the range where desilvering failure does not occur. Preferred time is 1 to 3 minutes
Minutes, more preferably 1 minute to 2 minutes. The treatment temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C. In the preferable temperature range, the desilvering rate is improved, and the stain generation after the processing is effectively prevented. The processing solution having a bleaching ability of the present invention is particularly preferably subjected to aeration during processing because the photographic performance is kept extremely stable. Means known in the art can be used for the aeration, and blowing of air into the processing liquid having a bleaching ability or absorption of air using an ejector can be performed. At the time of blowing air, it is preferable to discharge the air into the liquid through an air diffusing tube having fine pores. Such an air diffuser is widely used as an aeration tank in activated sludge treatment. Regarding aeration, Z-121, Eusing Process C-41 3rd edition (1982), Eastman Kodak Company, BL-1 to BL
-The items described on page 2 can be used. In the processing using the processing solution having the bleaching ability of the present invention, it is preferable that the stirring is intensified, and the practice is disclosed in JP-A-3-3384.
The contents described on page 8, upper right column, line 6 to lower left column, line 2 of Japanese Patent Publication No. 7 can be used as they are.

In the desilvering process, it is preferable that the stirring is strengthened as much as possible. Specific examples of the method for strengthening stirring include a method in which a jet of a processing solution is made to collide with the emulsion surface of a light-sensitive material described in JP-A-62-183460, and JP-A-62-1834.
A method of increasing the stirring effect using the rotating means of No. 61, and further moving the photosensitive material while bringing the emulsion surface into contact with the wiper blade provided in the liquid to make the emulsion surface turbulent, thereby further improving the stirring effect. Examples thereof include a method for improving the method and a method for increasing the circulation flow rate of the entire processing solution. Such a stirring improving means is effective in any of the bleaching solution, the bleach-fixing solution and the fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film and, as a result, increases the desilvering rate. Further, the above-mentioned stirring improving means is more effective when a bleaching accelerator is used, and it is possible to remarkably increase the accelerating effect and eliminate the fixing inhibiting action of the bleaching accelerator. The automatic developing machine used for the light-sensitive material of the present invention is disclosed in JP-A-60-191257, JP-A-60-191258, and JP-A-60-191258.
It is preferable to have the photosensitive material conveying means described in 60-191259. As described in the above-mentioned JP-A-60-191257, such a conveying means can remarkably reduce the carry-in of the treatment liquid from the front bath to the rear bath, and is highly effective in preventing the performance deterioration of the treatment liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The processing solution having a bleaching ability of the present invention is
The overflow solution after use in the treatment can be recovered, the components can be added to modify the composition, and then the overflow solution can be reused. Such usage is usually called regeneration, but the present invention can also favor such regeneration. For details of the reproduction, see Fuji Film Processing Manual issued by Fuji Photo Film Co., Ltd., Fuji Color Negative Film, CN-16 processing (revised August 1990), pp. 39-.
The matters described on page 40 can be applied. The kit for adjusting the processing solution having the bleaching ability of the present invention may be a liquid or a powder, but when the ammonium salt is excluded, most of the raw materials are supplied as a powder, and since the hygroscopicity is low,
Makes powder easier. From the viewpoint of reducing the amount of waste liquid, the regenerating kit is preferably a powder because it can be added directly without using excess water.

Regarding the regeneration of the processing solution having a bleaching ability,
In addition to the aeration mentioned above, "Basics of photographic engineering-silver salt photography-" (edited by the Photographic Society of Japan, published by Corona Publishing Co., 1979)
Year)) etc. can be used. Specifically, in addition to electric field regeneration, there is a method for regenerating bleaching solution with bromic acid, zincic acid, bromine, bromine precursor, persulfate, hydrogen peroxide, hydrogen peroxide using catalyst, bromic acid, ozone, etc. Can be mentioned.
In electrolytic regeneration, the cathode and the anode are put in the same bleaching bath, or the anode bath and the cathode bath are regenerated by using a diaphragm to separate the baths. The fixing solution can be reprocessed at the same time. The fixing solution and the bleach-fixing solution are regenerated by electrolytically reducing accumulated silver ions. Other,
It is also preferable to remove accumulated halogen ions with an anion exchange resin in order to maintain the fixing performance. Ion exchange or ultrafiltration is used to reduce the amount of washing water used, and it is particularly preferable to use ultrafiltration.

The light-sensitive material of the present invention is generally washed with water and / or stabilized after the desilvering process. The amount of rinsing water in the rinsing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, and further, the rinsing water temperature, the number of rinsing tanks (the number of stages), the replenishment system such as countercurrent and forward flow, and various other conditions. It can be set in a wide range. Of these, the relationship between the number of washing tanks and the water volume in the multi-stage countercurrent system is as follows.
e Society of MotionPicture and Tele-vision Engine
ers Vol. 64, pp. 248-253 (May 1955 issue). According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly 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, the method of reducing calcium ion and magnesium ion described in JP-A-62-288838 can be used very effectively as a solution to such a problem. In addition,
57-8,542, isothiazolone compounds, siabendazoles, chlorinated germicides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc. Hiroshi Horiguchi "Chemistry of Antibacterial and Antifungal Agents" (1986) Sankyo Published by Sanitation Technology Society, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982) Industrial Technology Association, Japan Society for Antibacterial and Antifungal "Encyclopedia of Antibacterial and Antifungal Agents" (1986
Year) can also be used.

Rinsing water in processing the light-sensitive material of the present invention
The pH is 4-9, preferably 5-8. The washing water temperature and the washing time can be variously set depending on the characteristics of the light-sensitive material, the use, etc., but in general, it is 20 seconds to 10 minutes at 15 to 45 ° C., preferably
A range of 30 seconds to 5 minutes at 25-40 ° C 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 stabilization treatment, all known methods described in JP-A-57-8543, JP-A-58-14834 and JP-A-60-220345 can be used.

In the stabilizing solution, compounds for stabilizing the dye image, for example, formalin, benzaldehydes such as m-hydroxybenzaldehyde, formaldehyde bisulfite adduct, hexamethylenetetramine and its derivative, hexahydrotriazine and its derivative, Examples include N-methylol compounds such as dimethylol urea and N-methylol pyrazole, organic acids and pH buffering agents. The addition amount of these compounds is preferably 0.001 to 0.02 mol per liter of the stabilizing solution, but the lower the free formaldehyde concentration in the stabilizing solution is, the less the formaldehyde gas is scattered, which is preferable. From this point of view, examples of the dye image stabilizer include m-hydroxybenzaldehyde, hexamethylenetetramine, N-methylolpyrazole, N-methylolazoles described in JP-A-4-270344, N, N'-bis (1 , 2,4-Triazol-1-ylmethyl) piperazine etc.
Azolylmethylamines described in 13753 are preferred. Particularly, azoles such as 1,2,4-triazole described in JP-A-4-359249 (corresponding to European Patent Publication No. 519190A2) and 1,4-bis (1,2,4)
The combined use of azolylmethylamine and its derivatives such as -triazol-1-ylmethyl) piperazine is preferable because of high image stability and low formaldehyde vapor pressure. In addition, if necessary, ammonium compounds such as ammonium chloride and ammonium sulfite, metal compounds such as Bi and Al, optical brighteners, hardeners, US Pat.
It is also preferable to contain an alkanolamine described in JP-A-86,583 or a preservative that can be contained in the fixing solution or the bleach-fixing solution, for example, a sulfinic acid compound described in JP-A-1-231510. .

The washing water and the stabilizing solution may contain various surfactants in order to prevent unevenness of water droplets during drying of the processed light-sensitive material. Among these, it is preferable to use a nonionic surfactant, and an alkylphenol ethylene oxide adduct is particularly preferable. Octyl, nonyl, dodecyl and dinonylphenol are particularly preferable as the alkylphenol, and 8 to 14 are particularly preferable as the number of moles of ethylene oxide added. Further, it is also preferable to use a silicon-based surfactant having a high defoaming effect.

Various chelating agents are preferably contained in the wash water and the stabilizing solution. Preferred chelating agents include aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N, N'-trimethylenephosphonic acid and diethylenetriamine-N, N,
Examples thereof include organic phosphonic acids such as N ', N'-tetramethylenephosphonic acid, and hydrolyzates of maleic anhydride polymers described in European Patent 345,172A1.

The overflow solution resulting from the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step. In the processing using an automatic processor, etc., when the above processing solutions are concentrated by evaporation,
In order to correct the concentration by evaporation, it is preferable to replenish an appropriate amount of water or a correction solution or a processing replenishing solution. The specific method for replenishing water is not particularly limited, but among them, a monitor water tank different from the bleaching tank described in JP-A-1-254959 and 1-254960 is installed, and water in the monitor water tank is installed. The amount of water vaporized in the bleaching tank is calculated from the amount of water vaporized in the bleaching tank, and the bleaching tank is replenished with water in proportion to the amount of water vaporized.
Nos. 3,249,644, 3,249,645 and 3,249,646, the evaporation correction method using a liquid level sensor and an overflow sensor are preferable.
As the water for correcting the evaporation of each treatment liquid, tap water may be used, but deionized water or sterilized water which is preferably used in the above washing step is preferably used.

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. In the present invention, each processing solution can be commonly used for processing two or more kinds of photosensitive materials. For example, by treating the color negative film and the color paper with the same treatment liquid, it is possible to reduce the cost of the processor and simplify the treatment.
The silver halide light-sensitive material of the present invention is disclosed in US Pat.
500,626, JP-A-60-133449, 5
It is also applicable to the photothermographic materials described in JP-A Nos. 9-218443, 61-238056, and European Patent 210,660A2.

[0115]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.

Example 1 Preparation of Emulsion 1 (Comparative Example: Cubic AgCl) 1200 ml of gelatin aqueous solution (gelatin 28
g, NaCl 4.0 g, and N, N'-dimethylimidazoline-2-thione (containing 3.2 ml of 1% aqueous solution) were added, the temperature was adjusted to 50 ° C, and 200.0 ml of AgNO ₃ aqueous solution was stirred ( AgNO ₃ (including 32.0 g) and N
200.0 ml of aCl aqueous solution (including 1.0 g of NaCl)
Was mixed for 24 minutes. Next, 526.7 ml of an AgNO ₃ aqueous solution (containing 158.0 g of AgNO ₃ ) and N were added.
526.7 ml of an aCl aqueous solution (containing 54.4 g of NaCl) was added and mixed while maintaining the temperature at 50 ° C over 26 minutes and 20 seconds. Then, the temperature was lowered to 30 ° C., and desalting and washing with water were carried out in the usual way. The obtained emulsion 1 is a cubic AgCl emulsion having a side length of 0.9 μm.

Preparation of Emulsion 2 (Emulsion of the present invention) 1200 ml of an aqueous gelatin solution (containing 20 g of deionized alkali-treated gelatin, pH 4.7) was placed in a reaction vessel, and while maintaining the temperature at 41 ° C., the solution was mixed with Ag-1 solution. Solution X-1 was simultaneously mixed and added in an amount of 12 ml at 50 ml / min. After stirring for 2 minutes, Ag-2 solution and X-2 solution at 22 ml at 62 ml / min.
Only simultaneous mixed addition. After stirring for 2 minutes, Ag-1 solution and X-1 solution were simultaneously mixed and added at 38 ml at 50 ml / min. Add 23 ml of NaCl-1 solution to adjust pH to 5.0,
The temperature was raised to 75 ° C. After ripening for 20 minutes, the temperature was lowered to 65 ° C. and the AgCl fine grain emulsion (average grain diameter of 0.
08 μm) was added at a rate of 4 × 10 ⁻³ mol / min AgCl addition, 10 minutes, and then 70 minutes by an accelerated addition method of AgCl10 ⁻⁴ mol / min. After the addition, the mixture was aged for 8 minutes, a precipitating agent was added, the temperature was lowered to 30 ° C., and the precipitate was washed with water.

However, Ag-1 solution is AgNO in 100 ml.
₃ 20 g, gelatin 0.8 g, HNO ₃ 1N solution 0.2ml
The X-1 solution contains NaCl 6.9 g, gelatin 0.8 g, and NaOH 1N solution 0.3 ml in 100 ml of Ag.
Solution-2 contains 2 g of AgNO ₃ in 100 ml, 0.8 g of the gelatin and 0.2 ml of HNO ₃ IN solution. Solution X-2 has 1.4 g of KBr in 100 ml, 0.8 g of the gelatin, N.
NaCl-1 solution containing 0.2 ml of aOH 1N solution is 100
10 ml of NaCl is contained in ml. The total projected area of tabular grains having an aspect ratio of 2 or more / the total projected area of all AgX grains of the obtained emulsion is 90%. The average aspect ratio (average diameter / average thickness) of tabular grains having an aspect ratio of 2 or more is 4.4
The average diameter of tabular grains with an aspect ratio of 2 or more is 0.9μ
m, and the average thickness was 0.2 μm. Water and gelatin were added to each emulsion to adjust the pH to 6.1 and pAg to 7.0, and then a sensitizing dye was added, followed by exposure to triethylthiourea and chloroauric acid at 55 ° C for 1/100 second of sensitivity. Was aged to be optimal.

[0119]

[Chemical 7]

After completion of the chemical sensitization, the compounds shown in Table 2 were added in small portions, and the following compounds were added to the triacetyl cellulose film support having an undercoat layer, and the mixture was coated with the protective layer by the simultaneous extrusion method. , A sample was obtained. (1) Emulsion layer-Emulsion ... Emulsion 1 (or Emulsion 2 is used) -Coupler 1-Tricresyl phosphate-Stabilizer 4-hydroxy-6-methyl-1,3,3
a, 7-Tetrazaindene ・ Coating aid sodium dodecylbenzene sulfonate (2) Protective layer ・ Polymethylmethacrylate fine particles ・ 2,4-dichloro-6-hydroxy-s-triazine sodium salt ・ Gelatin

[0121]

[Chemical 8]

These samples were exposed for sensitometry (1/100 second) and subjected to the following color development processing. (Processing step) Processing time Processing temperature Color development 45 seconds 38 ° C Bleach 30 seconds 38 ° C Fixing 45 seconds 38 ° C Stable (1) 20 seconds 38 ° C Stable (2) 20 seconds 38 ° C Stable (3) 20 seconds 38 ° C Dry 30 seconds 60 ° C. * Stability was a countercurrent system from (3) to (1).

The composition of the processing liquid is shown below. (Color developer) Ethylene dian tetraacetic acid 3.0 g 4,5-Dihydroxybenzene-1,3-disulfonic acid 2-sodium salt 0.3 g Potassium carbonate 30.0 g Sodium chloride 5.0 g Disodium-N, N-bis (Sulfonatoethyl) hydroxylamine 6.0 g 4- [N-ethyl-N- (β-hydroxylethyl) amino] -2-methylaniline sulfate 5.0 g Water was added to 1.0 liter pH (potassium hydroxide And adjusted with sulfuric acid) 10.00

(Bleaching Solution) 1,3-Diaminopropanetetraacetic acid ammonium ferric acid monohydrate 140 g 1,3-Diaminopropanetetraacetic acid 3 g Ammonium bromide 80 g Ammonium nitrate 15 g Hydroxyacetic acid 25 g Acetic acid (98%) 40 g Water was added. 1.0 liter pH (adjusted with aqueous ammonia and acetic acid) 4.3

(Fixer) Ethylenediaminetetraacetic acid disodium salt 15 g Ammonium sulfite 19 g Imidazole 15 g Ammonium thiosulfate (70 WT%) 280 ml Water was added to 1.0 liter pH (adjusted with ammonia water and acetic acid) 7.4

(Stabilizing Solution) Sodium p-toluenesulfinate 0.03 g Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.2 g Ethylenediamon tetraacetic acid disodium salt 0.05 g 1,2, 4-triazole 1.3 g 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 g Water was added to 1.0 liter pH (adjusted with ammonia water and acetic acid) 8.5

The density of the treated sample was measured with a green filter. Sensitivity is defined by the reciprocal of the exposure amount that gives a density of fog +0.2, and Sample 1 is compared to Sample 1 to Sample 5 to 13
On the other hand, the value of Sample 5 was expressed as a relative value with 100 as each. The values of sensitivity and fog are shown in Table 2 below.

[0128]

[Table 2]

As is clear from Table 2, the flat plate A of the present invention
Fog is more likely to occur in the gCl emulsion than in the conventionally well-known cubic AgCl emulsion. The compounds of the general formula (I) and the general formula (II) also suppress fog even in cubic AgCl, but the sensitivity is greatly reduced when fog is suppressed.
On the other hand, in the emulsion of the present invention, the compound of the general formula (I) does not significantly lower the sensitivity, and the fog is largely suppressed to about half. Further, when the compound of the general formula (II) is used in combination, the fog can be further suppressed,
A favorable result was obtained that the decrease in sensitivity at that time was not so great.

Example 2 Samples 5, 6, 8, 9, and 10 were stored at 40 ° C. and 80% for 5 days, and then subjected to the same color development process as in Example 1. Table 3 shows the change in the reciprocal of the exposure amount (logarithmic display) that gives a density of fog +0.2 before and after storage.

[0131]

[Table 3]

As is clear from Table 3, the present invention significantly improved the sensitivity change during storage.

Claims (2)

[Claims] 1. A total of tabular silver halide grains having two parallel main planes (100) faces, an aspect ratio of 1.5 or more and a silver chloride content of 60 mol% or more. A silver halide emulsion comprising 50% or more of the projected area of a grain and containing a compound represented by the following general formula (I). [Chemical 1] In the formula, R ¹ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ² is a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, an alkenyl group, an alkynyl group or an alkoxy group. A group or an electron-withdrawing group, and n
When 2 is 2 or more, plural R ^{2 s} may be the same or different, and R ^{2 s} may be linked to each other to form a condensed ring. R ³ is a hydrogen atom or an optionally substituted alkyl group, alkenyl group, or aralkyl group, and X ⁻
Is an anion, and n is 0 or 1 to 3. 2. The silver halide emulsion according to claim 1, wherein the silver halide emulsion further contains at least one mercaptotetrazole.