JPH06250312A - Preparation of seed-crystal emulsion, silver halide emulsion and photographic sensitive material - Google Patents

Abstract

PURPOSE:To stably prepare a silver halide emulsion consisting of a high aspect ratio plate grain and to provide a highly sensitive photographic sensitive material contg. the emulsion and excellent in preservation stability. CONSTITUTION:A silver halide emulsion, in which the plate silver halide grains having >=2 aspect ratio occupy 50-100% of the projected area of all the silver halide grains, is desalted and used as the seed crystal emulsion. Besides, a silver halide emulsion, in which the plate silver halide grains having >=3 aspect ratio occupy 50-100% of the projected area of all the silver halide grains, is prepared by using at least one kind of silver oxidizing agent. A silver halide color photographic sensitive material having at least one emulsion layer contg. the emulsion thus obtained on a substrate is prepared.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a method for preparing a seed crystal emulsion,
The present invention relates to a silver halide emulsion and a photographic light-sensitive material.

[0002]

2. Description of the Related Art Recent technical trends of silver halide color photographic light-sensitive materials include the pursuit of higher sensitivity represented by ISO 1600 photographic light-sensitive materials, and the smaller format such as 110 size system and disk size system. Applicable to the photosensitivity material used for shooting with a camera, for example, the photosensitivity material used for filming with a lens such as "Sharp Run Hi" and "Sharp Run Panoramic" (trade name) In addition, there is a demand for photosensitive materials having graininess, sharpness, and color reproducibility, and higher performance requirements are being made for each performance.

In response to such demands, tabular grains intended to improve sensitivity including improvement of color sensitizing efficiency by a sensitizing dye, improve sensitivity / granularity relationship, sharpness, and covering power. The technique used in US Pat.
No. 434, 226, No. 4,414, 310, No. 4, 4
33,048, 4,414,306, 4,45
9,353, JP-A-58-113927, 59-59.
No. 119350.

The conventional method for preparing tabular grains is described in, for example, JP-A Nos. 58-113927 and 58-1139.
28, 58-127921, JP-A 1-1584.
The description of No. 26 can be referred to.

As a method of forming silver halide grains, there is a method of growing separately prepared seed grains, a so-called seed crystal method. By adopting the seed crystal method,
Shorten the particle formation process, stabilize manufacturing variability, and
By using monodisperse seed crystal grains, an effect that tabular grains having improved monodispersity can be prepared can be expected.

As such a seed crystal method, for example, Japanese Patent Publication No. 3-46811 discloses a particle forming method using a spherical seed crystal. However, this method does not yield high aspect ratio final particles.

Further, JP-A-61-112142 and JP-A-6-112142.
Nos. 2-58237 and 55-142329 disclose grain forming methods using multiple twin grains. This method is suitable for preparing tabular grains with high aspect ratio,
Unless the desalted and redispersed seed crystals are grown promptly, performance fluctuations occur, which is a problem in terms of stable production.

As described above, the conventional seed crystal method has not realized stable production of tabular grains having a high aspect ratio, and further improvement has been desired.

Further, JP-A-3-196136 and JP-A-3-196136.
No. 196137 discloses a technique of forming grains in the presence of an oxidizing agent for silver, but no example of applying this technique to the preparation of seed crystal emulsion is known.

[0010]

An object of the present invention is to provide a technique for stably preparing tabular grains having a high aspect ratio. Specifically, it is to provide a method for preparing a twinned seed crystal emulsion suitable for preparing the tabular grains.

Another object of the present invention is to prepare a silver halide emulsion prepared by using the emulsion, a photographic light-sensitive material containing the same, which has high sensitivity and excellent storage stability (silver halide color photographic light-sensitive material). ) Is to provide.

[0012]

The above object of the present invention is achieved by the following items (1) and (2).

(1) A method for preparing a seed crystal emulsion, which comprises using at least one oxidizing agent for silver.

(2) A method for preparing a seed crystal emulsion, which comprises using at least one compound represented by the following general formula (I), (II) or (III).

[0015]

[Chemical 4] In the formula, R, R ¹ and R ² may be the same or different,
It represents an aliphatic group, an aromatic group, or a heterocyclic group, and M represents a cation. L represents a divalent linked value, and m is 0 or 1.

The compounds of the general formulas (I) to (III) are
It may be a polymer containing a divalent group derived from the structures represented by (I) to (III) as a repeating unit. Further, if possible, R, R ¹ , R ² and L may be bonded to each other to form a ring.

Another object of the present invention is achieved by the following (3) to (10).

(3) A silver halide emulsion prepared by using desalted silver halide grains as a seed crystal emulsion, wherein at least one oxidizer for silver is added during the step of preparing the seed crystal emulsion. A silver halide emulsion characterized by using a seed.

(4) A silver halide emulsion prepared by using desalted silver halide grains as a seed crystal emulsion, wherein a silver halide emulsion represented by the following general formula ( A silver halide emulsion characterized by using at least one compound represented by I), (II) or (III).

[0020]

[Chemical 5] In the formula, R, R ¹ and R ² may be the same or different,
It represents an aliphatic group, an aromatic group, or a heterocyclic group, and M represents a cation. L represents a divalent linking group, and m is 0 or 1.

The compounds of the general formulas (I) to (III) are
It may be a polymer containing a divalent group derived from the structures represented by (I) to (III) as a repeating unit. Further, if possible, R, R ¹ , R ² and L may be bonded to each other to form a ring.

(5) The tabular silver halide grains having an aspect ratio of 2 or more are 50 to 50% of the projected area of all the silver halide grains.
A tabular silver halide grain having an aspect ratio of 3 or more prepared by desalting a silver halide emulsion occupying 100% and then used as a seed crystal emulsion has 50 to 50% of the projected area of all silver halide grains. A silver halide emulsion comprising 100% of a silver halide emulsion, wherein at least one oxidizing agent for silver is used in the step of preparing the seed crystal emulsion.

(6) The tabular silver halide grains having an aspect ratio of 2 or more are 50 to 50% of the projected area of all the silver halide grains.
A tabular silver halide grain having an aspect ratio of 3 or more prepared by desalting a silver halide emulsion occupying 100% and then used as a seed crystal emulsion has 50 to 50% of the projected area of all silver halide grains. A silver halide emulsion occupying 100%, wherein at least one compound represented by the following general formula (I), (II) or (III) is added during the step of preparing the seed crystal emulsion. A silver halide emulsion characterized in that

[0024]

[Chemical 6] In the formula, R, R ¹ and R ² may be the same or different and each represents an aliphatic group, an aromatic group, or a heterocyclic group, and M represents a cation. L represents a divalent linking group, and m is 0 or 1.

The compounds of the general formulas (I) to (III) are
It may be a polymer containing a divalent group derived from the structures represented by (I) to (III) as a repeating unit. Further, if possible, R, R ¹ , R ² and L may be bonded to each other to form a ring.

(7) A photographic light-sensitive material having at least one silver halide emulsion layer containing the silver halide emulsion described in (3) on a support.

(8) A photographic light-sensitive material having at least one silver halide emulsion layer containing the silver halide emulsion described in (4) on a support.

(9) A photographic light-sensitive material having at least one silver halide emulsion layer containing the silver halide emulsion described in (5) on a support.

(10) A photographic light-sensitive material having at least one silver halide emulsion layer containing the silver halide emulsion described in (6) on a support.

The present invention will be described in detail below.

The steps of preparing a silver halide emulsion in the present invention are roughly classified into a step of preparing seed crystal grains (seed crystal emulsion) and a step of growing seed crystal grains.

Here, the step of preparing the seed crystal particles includes nucleation and
It consists of a grain formation process including aging and growth, followed by a desalination water washing process and a refrigerating storage or frozen storage process.

The step of growing seed crystal particles includes the step of further growing particles in the presence of the seed crystal particles,
The process consists of desalination and chemical sensitization.

The oxidizing agent for silver used in the method for preparing a seed crystal emulsion of the present invention means a compound having an action of acting on metallic silver and converting it into silver ion. In particular, a compound that converts extremely minute silver atoms, which are a by-product in the process of forming silver halide grains, into silver ions is effective. The silver ion generated here may form a poorly soluble silver salt such as silver halide, silver sulfide or silver selenide, or may form a readily soluble silver salt such as silver nitrate. May be.

The oxidizing agent for silver may be an inorganic substance or an organic substance.

As the inorganic oxidant, for example, ozone,
Hydrogen peroxide and its adducts (eg 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 · 2
H ₂ O), 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 acids such as chromates (e.g., K ₂ Cr ₂ O ₇₎ Salts, halogen elements such as iodine and bromine, perhalogenates (eg potassium periodate) salts of high valent metals (eg potassium hexacyanoferrate) and thiosulphonates.

As the organic oxidizing agent, quinones such as p-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 oxidants of thiosulfonates, and organic oxidants of quinones.

A more preferable oxidizing agent is thiosulfonate, which can be selected from the compounds represented by the above-mentioned compounds (I) to (III).

In the method of preparing a seed crystal emulsion of the present invention, at least one of the oxidizing agents for silver is added during the preparation step. Here, “during the preparation step” basically means that any step may be performed. Particularly preferred is the method of adding during grain formation. Further, a method of adding to the desalted water washing step is also preferable.

It may be added to the reaction vessel in advance, but a method of adding it at an appropriate time for grain formation is preferred. Alternatively, the water-soluble silver salt or the water-soluble alkali halide may be added with an oxidizing agent for silver in advance, and these aqueous solutions may be used to form particles. In addition, it is also preferable to add it in several times along with the formation of particles or to continuously add it for a long time.

The additive of the oxidizing agent to silver is preferably 10 ^-7 to 10 ^-1 mol per mol of silver halide, and 10 ^-6 mol.
To 10 ^-2 mol is more preferable, and 10 ^-5 to 10 ^-3 mol is most preferable.

In order to add the oxidizing agent for silver during the step of preparing the seed crystal emulsion, a method usually used for adding an additive to a photographic emulsion can be applied. Specifically, the water-soluble compound is an aqueous solution having a suitable concentration, and the water-insoluble or sparingly-soluble compound is a suitable organic solvent miscible with water, for example, alcohols, glycols, ketones, esters, Among the amides, they can be dissolved in a solvent that does not adversely affect the photographic characteristics and added as a solution.

The thiosulfonic acid compounds represented by the general formulas (I), (II) and (III) will be described in more detail.
When R, R ¹ and R ² are aliphatic groups, they are saturated or unsaturated, linear, branched or cyclic, aliphatic hydrocarbon groups, preferably alkyl groups having 1 to 22 carbon atoms, Is 2
To 22 alkenyl groups and alkynyl groups, which may be further substituted.

Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, hexadecyl, octadecyl, cyclohexyl, isopropyl,
t-butyl is mentioned.

Examples of the alkenyl group include allyl and butenyl. Examples of the alkynyl group include propargyl and butynyl.

When R, R ¹ and R ² are aromatic groups,
Included are monocyclic or fused ring aromatic groups. An aromatic group having 6 to 20 carbon atoms is preferable, and examples thereof include phenyl and naphthyl. These may be further substituted.

When R, R ¹ and R ² are heterocyclic groups, they have at least one element selected from nitrogen, oxygen, sulfur, selenium and tellurium and have at least 1 carbon atom.
It has a 3- to 15-membered ring. Preferably 3
A 6-membered heterocycle, for example, pyrrolidine, piperidine, pyridine, tetrahydrofuran, thiophene, oxazole, thiazole, imidazole, benzothiazole, benzoxazole, benzimidazole, selenazole, benzoselenazole, tellurazole, triazole, benzotriazole. , Tetrazole, oxadiazole and thiadiazole.

Substituents for R, R ¹ and R ² include, for example, alkyl groups (eg, methyl, ethyl, hexyl),
Alkoxy group (eg, methoxy, ethoxy, octyl), aryl group (eg, phenyl, naphthyl, tolyl), hydroxy group, halogen atom (eg, fluorine,
Chlorine, bromine, iodine), aryloxy group (eg, phenoxy), alkylthio group (eg, methylthio, butylthio), arylthio group (eg, phenylthio), acyl group (eg, acetyl, propionyl, butyryl,
Valeryl), sulfonyl group (for example, methylsulfonyl, phenylsulfonyl), acylamino group (for example,
Acetylamino, benzoylamino), sulfonylamino groups (eg methanesulfonylamino, benzenesulfonylamino), acyloxy groups (eg acetoxy,
Benzoxy), carboxyl group, cyano group, sulfo group,
Amino group, -SO ₂ SM group, (M is a monovalent shows a cation) -SO ₂ R ¹ group (R ¹ is the same) and the like.

As the divalent linking group represented by L,
An atom or atomic group containing at least one selected from C, N, S and O can be mentioned. As a concrete example,
Alkylene group, alkenylene group, alkynylene group, arylene group, -O-, -S-, -NH-, -CO-, -S.
O ₂ − and the like may be used alone or in combination.

L is preferably a divalent aliphatic group or a divalent aromatic group. When L is a divalent aliphatic group, specific examples thereof include the following groups and xylylene groups.

[0052]

[Chemical 7] When L is a divalent aromatic group, specific examples thereof include:
Examples thereof include a phenylene group and a naphthylene group.

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

M is preferably a metal ion or an organic cation. Examples of the metal ion include lithium ion, sodium ion and potassium ion. Examples of organic cations include ammonium ions (for example, ammonium, tetramethylammonium,
Tetrabutylammonium), phosphonium ions (eg, tetraphenylphosphonium), and guanidyl groups.

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

[0056]

[Chemical 8] These polymers may be homopolymers or copolymers with other copolymerizable monomers.

Specific examples of the compound represented by formula (I), (II) or (III) are shown in Table A below, but the invention is not limited thereto.

The compounds of the general formula (I), (II) or (III) are described in JP-A-54-1019; British Patent 972,211;
Journal of Organic Chemis
try (Journal of Organic Chemistry) 53, 396 (1988) and Chemica.
l Abstracts (Chemical Abstracts)
It can be easily synthesized by the method described or cited in Volume 59, 9776e.

The most preferable compound for the present invention is the compound represented by the general formula (I).

[0060]

[Chemical 9]

[0061]

[Chemical 10]

[0062]

[Chemical 11]

[0063]

[Chemical 12]

[0064]

[Chemical 13]

[0065]

[Chemical 14]

[0066]

[Chemical 15]

[0067]

[Chemical 16] The silver halide grains constituting the seed crystal emulsion prepared in the present invention are preferably tabular grains having twin planes.

The tabular grain is a generic term for grains having one twin plane or two or more parallel twin planes. In this case, the twin plane means the (111) plane when ions at all lattice points on both sides of the (111) plane have a mirror image relationship.

The tabular seed crystal emulsion prepared in the present invention has, for example, an aspect ratio (diameter of circle equivalent of silver halide grain / grain thickness) of 2.0 or more, preferably 2.0 or more and 15.0 or less, and particularly preferably. Is an emulsion of tabular grains of 3.0 or more and 10.0 or less, and the grains have a projected area of 50% or more, preferably 70% or more, particularly preferably 70% or more of the projected area of all silver halide grains in the emulsion. It is an emulsion in which 85% or more is present. The average spherical equivalent diameter of the tabular seed crystal particles is preferably 0.4 μ or less, particularly preferably 0.15 μ or more and 0.3 μ or less, and the average particle thickness of the tabular seed crystal particles is 0.2 μ or less. It is preferably 0.15 μ or less and particularly preferably.

The tabular seed crystal grains may be any of silver bromide, silver iodobromide, silver chloride, silver chlorobromide, silver iodochlorobromide and silver iodochloride.

The tabular seed crystal grains of the present invention may have at least two layered structures having substantially different halogen compositions, or may have a uniform composition.

The particles having a layered structure having different halogen compositions are those having a high iodine layer in the core portion and a low iodine layer in the outermost layer, or those having a low iodine layer in the core portion and a high iodine layer in the outermost layer. It may be.

The particle size distribution may be narrow or wide.

A method for preparing the tabular seed crystal grains (seed crystal emulsion) of the present invention will be described.

The present invention includes a step of forming tabular core grains by simultaneously mixing a water-soluble silver salt and a halide salt aqueous solution in a reaction vessel containing an aqueous gelatin solution and further aging.

The following are preferable conditions for forming the flat plate nuclei in the present invention.

1) The gelatin concentration is 0.8 to 20.
wt%, preferably 1.0 to 15 wt%,
More preferably, 1.0 to 6 wt% is effective, and as the gelatin species used, ordinary photographic gelatin is preferable. However, at temperatures below 35 ° C, high concentrations (1.6
(~ 20 wt%) gelatin solution is difficult to use because it is set. At such temperatures, it is particularly preferable to use low molecular weight gelatin (molecular weight 2000 to 100,000), modified gelatin such as phthalated gelatin, and gelatin that is difficult to set such as gelatin taken from fish skins living in the cold sea. preferable.

2) As an addition amount mixing device for improving stirring, US Pat. No. 3,785,777 (1974)
And German Patent Applicatio
n (OLS) No. An apparatus for adding and mixing the reaction solution in the liquid is preferable, such as the apparatus described in 2,556,888.

3) The addition rate of silver salt and halide salt was 6 × 10 6 per 1 liter of aqueous gelatin solution.
^-4 mol / min to 2.9 × 10 ^-1 mol / min.

4) Ordinary photographic gelatin is used as the gelatin added to the silver salt or halide salt aqueous solution to be added, but the concentration can be added within a range where the aqueous solutions are not set, and usually 0.05 to 1 .6 wt%
Is. However, if a heating device for those liquids is attached,
Higher concentrations (about 20 wt%) can be added.

Further, in this case, gelatin such as low molecular weight gelatin (molecular weight 2000 to 100,000) or modified gelatin is difficult to set as the gelatin seed, and thus it is particularly preferable.

When gelatin is added to this silver salt or halide salt aqueous solution, the gelatin species, concentration and temperature should be the same as those in the reaction vessel. It is more preferable because it can be kept uniform and more uniform nucleation can be performed.

5) The Br ^- concentration in the reaction solution is p
Br can be set to 1.0 to 2.5.

6) As the irrelevant salt concentration in the reaction solution,
It can be set in the range of 1.0 × 10 ^{-2 to 1} mol / liter, more preferably 1 × 10 ^{-1 to 1} mol / liter.

A silver halide solvent is useful for promoting the ripening of the silver halide grains. For example, it is known to have excess halogen ions present in the reactor to accelerate aging. It is therefore clear that introduction of an aqueous halide solution into the reactor can accelerate aging. Also, other ripening agents can be used.
The total amount of these ripening agents can be added to the dispersion medium in the reactor before adding the silver salt and the halide salt, and one or more halide salts, silver salts or peptizers can be added. It is also possible to add the agent and introduce it into the reactor. The ripening agent can also be introduced independently at the halide salt and silver salt addition stages.

As the ripening agents other than the halogen ions, ammonia, amine compounds, thiocyanate salts such as alkali metal thiocyanate salts, especially sodium and potassium thiocyanate salts, and ammonium thiocyanate salts can be used. The use of thiocyanate ripening agents is described, for example, in US Pat.
No. 264, No. 2,448,534 and No. 3,32
No. 0,069. Also, US Pat.
Known thioether ripening agents such as those described in Nos. 71,157, 3,574,628, and 3,737,313 can also be used. Alternatively, JP-A-5
It is also possible to use thione compounds as disclosed in 3-82408 and 53-144319.

The present invention also includes the step of growing the tabular seed crystal grains thus obtained.

In the grain growth process, it is desirable to add silver and halogen solutions so that new crystal nuclei are not generated. The size of the emulsion grains can be adjusted by controlling the temperature, selecting the type and amount of the solvent, and controlling the addition rate of the silver salt and halide used during grain formation.

In addition, part or all of the silver added in the grain growth process can be supplied as fine silver halide grains as described in JP-A-62-99751.

The tabular seed crystal grains (seed crystal emulsion) of the present invention are
It can be prepared by referring to a known method for preparing a tabular silver halide emulsion except that the method for using a silver salt specified in the present invention is followed. As a method for preparing a silver halide seed crystal emulsion composed of tabular grains, for example, Duffin
(Duffin), "Photographic Emu"
Ision Chemistry ”(Focal Pr
ess, New York 1966) pp. 66-7
Page 2, and A. P. H. Trivelli, W.W. F. Smith edition "Phot.J
pp. 285, pp. 285, pp. 1985, No. 58-113927, and No. 58-11.
It is also possible to refer to the methods described in Nos. 3928 and 58-127921.

In addition to these, for example, Cleeve's Theory and Practice of Photography (Cleve, Photogra
phy Theory and Practice (1
930)), p. 131; Gatov, Photography.
Science and Engineering (Gutof
f, Photographic Science an
dEngineering), Volume 14, 248-25
P. 7 (1970); U.S. Pat. No. 4,434,226.
Issue No. 4,414,310 Issue No. 4,433,048
No. 4,439,520, British Patent No. 2,112,
157, Japanese Patent Application Nos. 3-280961 and 3-1122.
The methods described in No. 59 and No. 3-119081 can be referred to.

In the present invention, it is essential that the tabular seed crystal grains are washed with water for desalting and dispersed in a newly prepared protective colloid. The washing temperature can be selected according to the purpose,
It is preferable to select in the range of 5 to 50 ° C. PH when washing with water
Can also be selected according to the purpose, but it is preferably selected in the range of 2 to 10. More preferably, it is in the range of 3-8. The pAg at the time of washing with water can be selected according to the purpose, but it is preferably selected within the range of 5 to 10. As a method of washing with water, a noodle washing method, a dialysis method using a semipermeable membrane, a centrifugation method, a coagulation sedimentation method, or an ion exchange method can be selected and used. The coagulation sedimentation method can be selected from, for example, a method using a sulfate, a method using an organic solvent, a method using a water-soluble polymer, and a method using a gelatin derivative.

The seed crystal emulsion prepared as described above is refrigerated or frozen. The storage temperature is preferably 5 ° C or lower.

Next, a process including growth of seed crystal grains prepared as described above will be described.

The step including the growth of seed crystal grains is, for example,
The process further comprises the steps of further growing the particles in the presence of the seed crystal particles described above, washing with demineralized water and chemical sensitization. The amount of seed crystals used at this time is arbitrary, but it is preferable to use the seed crystals in an amount corresponding to 1/10 or less of the silver molar amount of the silver salt supplied for growth. , And more preferably 1/2
It is 0 or less, particularly preferably 1/25 or less. Although any time can be selected from the time when the seed crystal is prepared until the time when it is used for growth, it is preferably used for growth after being refrigerated for one day or more.

The growth in the presence of the seed crystal can be performed in the same manner as the growth in the seed crystal preparation described above.

The tabular silver halide grains (tabular silver halide emulsion) prepared from the seed crystal grains (seed crystal emulsion) in the present invention will be described.

Also in this case, the tabular grain is a general term for grains having one twin plane or two or more parallel twin planes. In this case, the twin plane is defined as (1) when the ions at all lattice points on both sides of the (111) plane have a mirror image relationship.
11) It means a surface.

Also in the tabular silver halide grains, the aspect ratio means the ratio of the diameter to the thickness of the silver halide grains as described above. That is, it is a value obtained by dividing the diameter of each silver halide grain by the thickness. Here, the diameter means the diameter of a circle having an area equal to the projected area of a grain when the silver halide emulsion is observed with a microscope or an electron microscope. Therefore, the aspect ratio of 3 or more means that the diameter of this circle is 3 times or more the thickness of the particles.

As an example of the method of measuring the aspect ratio, there is a method of taking a transmission electron microscope photograph by the replica method and obtaining the equivalent circle diameter and thickness of each particle. In this case, the thickness is calculated from the length of the shadow of the replica.

The tabular silver halide emulsion prepared in the present invention has, for example, an average aspect ratio of 3.0 or more, preferably 3.0 or more and 25 or less, particularly preferably 4.0 or more 2.
An emulsion in which 0 or less silver halide grains are present in 50% or more of the projected area of all silver halide grains in the emulsion, preferably 70% or more, and particularly preferably 85% or more. In this tabular silver halide grain, the average equivalent spherical diameter is preferably 0.2 µ or more, particularly preferably 0.3 µ or more and 3.0 µ or less, and the average grain thickness is 0.05 µ or more and 0.5 µm. The following is preferable.

The tabular silver halide grains prepared in the present invention may be any of silver bromide, silver iodobromide, silver chloride, silver chlorobromide, silver iodochlorobromide and silver iodochloride. .

The tabular silver halide grains prepared in the present invention may have at least two layered structures having substantially different halogen compositions or have a uniform composition.

With respect to grains having a layered structure having different halogen compositions, even an emulsion containing a high iodine layer in the core part and a low iodine layer in the outermost layer can be a grain containing a low iodine layer in the core part and a high iodine layer in the outermost layer. It may be. Furthermore, the layered structure is 3
It may consist of more than one layer and preferably has a lower iodine as it is located on the outside.

In the preparation of the tabular silver halide emulsion of the present invention, the properties of silver halide grains can be controlled by allowing various compounds to be present in the silver halide precipitation forming process. Such a compound may be initially present in the reaction vessel, or may be added together with one or more salts by a conventional method. US Patent Nos. 2,448,060, 2,628,167, 3,737,313, 3,772,031, and Research Disclosure (hereinafter abbreviated as RD), 134 volumes. , June 1975, 13452, and compounds such as compounds of copper, iridium, lead, bismuth, cadmium, zinc (chalcogen compounds such as sulfur, selenium and tellurium), gold and Group VIII noble metals. The properties of the silver halide grains can be controlled by allowing them to exist during the silver halide precipitation formation process.

In the present invention, it is preferable that the silver halide emulsion is subjected to reduction sensitization during grain formation, after grain formation and before chemical sensitization other than reduction sensitization, during chemical sensitization, or after chemical sensitization.

Here, reduction sensitization is a method of adding a reduction sensitizer to a silver halide emulsion, pAg1 called silver ripening.
Method for growing or ripening silver halide grains in a low pAg atmosphere of ~ 7, pH 8 to 1 called high pH ripening
1 is a method of growing or aging in a high pH atmosphere. Also, two or more of these methods can be used together.

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

Known reduction sensitizers are, for example, stannous salts, ascorbic acid and its derivatives, amines and polyamines, hydrazine derivatives, formamidinesulfinic acid, silane compounds and borane compounds. As the reduction sensitizer used in the present invention, these known reduction sensitizers can be selected and used, or two or more compounds can be used in combination. Preferred compounds as the reduction sensitizer used in the present invention are stannous chloride, thiourea dioxide,
Dimethylamine borane, ascorbic acid and its derivatives. The addition amount of the reduction sensitizer in the present invention needs to be selected depending on the emulsion production conditions, but is suitably in the range of 10 ^-7 to 10 ^-3 mol per mol of silver halide.

The reduction sensitizer may be added during grain growth in the state of being dissolved in a solvent such as water or alcohols, glycols, ketones, esters, amides. Although it can be added to the reaction vessel in advance, a method of adding it at an appropriate time during the growth of silver halide grains is preferable. In addition, a reduction sensitizer is added in advance to an aqueous solution of a water-soluble silver salt or a water-soluble alkali halide,
These aqueous solutions can also be used to precipitate silver halide grains. In addition to this, a solution of the reduction sensitizer is added in several portions along with the growth of silver halide grains,
Alternatively, continuous addition for a long time is also a preferable method.

In the present invention, for silver halide emulsions,
For example, European Patent Nos. 96,727B1 and 64,41.
2B1 to provide roundness to the particles, or West German Patent 2,306,447C2,
The particle surface may be modified as disclosed in JP-A-60-221320.

In the silver halide emulsion of the present invention, the grain surface generally has a flat structure.
In some cases, it is preferable to intentionally form irregularities. Examples thereof include grains having a part of a crystal, for example, grains having a hole at the apex or the center of the face, as described in JP-A-58-106532 and JP-A-60-221320, or US Pat. Raffle particles described in 4,643,966 are mentioned.

The tabular grains in the emulsion prepared in the present invention preferably have dislocation lines. This dislocation is a dislocation linearly introduced in a particular direction of the crystal orientation of the grain, a curved dislocation, a dislocation introduced throughout the grain, or a dislocation introduced only in a particular part of the grain. , (For example, dislocations introduced only in the fringe portion of the grain).

The emulsion prepared in the present invention may be a so-called polydisperse emulsion in which the size distribution of silver halide grains is wide depending on the purpose, or a monodisperse emulsion in which the size distribution is narrow. As a scale for expressing the size distribution of silver halide grains, there is a case where a coefficient of variation of a projected area circle equivalent diameter of a grain or a sphere equivalent diameter of a volume is used. In the case of a monodisperse emulsion, an emulsion having a grain size distribution having a coefficient of variation of 25% or less, more preferably 20% or less, still more preferably 15% or less is preferable.

The tabular silver halide emulsion prepared in the present invention can be subjected to chemical sensitization represented by sulfur sensitization and gold sensitization. The location of chemical sensitization differs depending on the composition, structure, and shape of the emulsion grains and the intended use of the emulsion. In some cases, the chemically sensitized nuclei are embedded in the grain, at a shallow position from the grain surface, or in some cases the chemically sensitized nuclei are formed on the surface. The effect of the present invention is effective in any case, but particularly preferable is the case where a chemical sensitizing nucleus is formed near the surface. That is, the surface latent image type emulsion is more effective than the internal latent image type emulsion.

Chemical sensitization is performed by James (TH Jam
es), The Photographic Process, 4th
Edition, published by Macmillan, 1977, (TH Jame
s, The Theory of the Photo
graphic Process, 4th ed, M
Acmillan, 1977) 67-76, and using active gelatin, or Research Disclosure, 120, 1974.
April, 2008; Research Disclosure,
34, June 1975, 13452, U.S. Pat. No. 2,
642, 361, 3,297,446, 3,7
72,031, ibid 3,857,711, ibid 3,90
1,714, 4,266,018 and 3,9
04,415 and British Patent No. 1,315,755.
, PAg 5-10, pH 5-8 and temperature 30-80 ° C.
It can be carried out using gold, platinum, palladium, iridium or a combination of plural sensitizers.

As the gold sensitizer used in the present invention, a gold complex salt (see, for example, US Pat. No. 2,399,083) is particularly preferable.

Of these, potassium chloroaurate, potassium aurithiocyanate, auric trichloride, sodium aurithiosulfate, and 2-aurosulfobenzothiazolemethochloride are particularly preferable.

The content of the gold sensitizer in the silver halide grain phase is preferably 10 ^-9 to 10 ^-3 mol, and more preferably 10 ^-8 to 10 ^-4 mol per mol of silver halide.

Examples of the sulfur sensitizer used in the present invention include thiosulfates, thioureas, thiazoles, rhodanines, and other compounds (specific examples; US Pat. No. 1,574,741).
No. 944, No. 2,410,689, No. 2,27
No. 8,947, No. 2,728,668, No. 3,6
56,955, 4,030,928, 4,
No. 067,740), and among these, thiosulfates, thioureas and rhodanins are particularly preferable.

The amount of the sulfur sensitizer can be selected optimally depending on the conditions such as the grain size, the temperature of chemical sensitization, pAg and pH. Specifically, it is used in an amount of 10 ⁻⁷ to 10 ⁻³ mol, preferably 5 × 10 ⁻⁷ to 10 ⁻⁴ mol, and more preferably 5 × 10 ⁻⁷ to 10 ⁻⁵ mol, per mol of silver halide.

The temperature of chemical sensitization can be appropriately selected within the range of 30 ° C. to 90 ° C., pAg of 5 or more and 10 or less, and pH of 4 or more.

In addition, in the present invention, iridium,
Sensitization methods using metals such as platinum, rhodium, and palladium (see, for example, US Pat. Nos. 2,448,060 and 2,56).
No. 6,245, No. 2,566,263), a selenium sensitizing method using a selenium compound, and a tellurium sensitizing method using a tellurium compound can be used in combination.

It is also possible to carry out chemical sensitization in the presence of a chemical sensitization aid. Here, as the chemical sensitization aid, compounds such as azaindene, azapyridazine, and azapyrimidine that are known to suppress fog and increase sensitivity in the process of chemical sensitization are used. Examples of chemical sensitization aid modifiers are:
US Pat. Nos. 2,131,038 and 3,411,91
No. 4, 3,554, 757, JP-A-58-1265.
No. 26, and Duffin, "Photoemulsion Chemistry", 138.
~ Page 143.

In the present invention, the silver halide emulsion may be spectrally sensitized with a methine dye or the like. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are
Cyanine dyes, merocyanine dyes, and composite merocyanine dyes. Any of the nuclei normally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. For example, pyrroline nucleus, oxazoline nucleus, thiozoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus,
A tetrazole nucleus, a pyridine nucleus; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and a nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, for example, indolenine nucleus, benzindolenine nucleus, indole nucleus, Benzoxadol nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus can be applied. These nuclei may be substituted on carbon atoms.

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

These sensitizing dyes may be used alone or in combination. Combinations of sensitizing dyes are 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, 3,52
No. 2,052, No. 3,527,641, No. 3,61
7,293, 3,628,964, 3,66
6,480, 3,672,898, 3,67
9,428, 3,703,377 and 3,76
9,301, 3,814,609, 3,83
No. 7,862, No. 4,026,707, British Patent Nos. 1,344,281, 1,507,803, Japanese Patent Publication No. 43-4936, No. 53-12,375, and Japanese Unexamined Patent Publication No. 52-375. -110,618 and 52-109,925.

Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a substance which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion.

The dye may be added to the emulsion at any stage in the emulsion preparation which has heretofore been known to be useful. Most commonly, it is carried out after the completion of chemical sensitization and before coating, but it is described in US Pat. No. 3,628,9.
No. 69 and No. 4,225,666, the spectral sensitization can be performed simultaneously with the chemical sensitization by adding the chemical sensitizer at the same time as described in JP-A-58-113,92.
It can be carried out prior to chemical sensitization as described in No. 8 or it can be added before the completion of silver halide grain precipitation to initiate spectral sensitization. It is also possible to add these said compounds separately, as taught in U.S. Pat. No. 4,225,666, i.e. to add some of these compounds prior to chemical sensitization and the rest to chemical sensitization. It is also possible to add after sensation and such addition may be done at any time during silver halide grain formation, as taught in US Pat. No. 4,183,756.

The addition amount is 4 × per mol of silver halide.
It may be 10 ⁻⁶ to 8 × 10 ⁻³ mol.

Gelatin is advantageously used as a protective colloid used in the preparation of the silver halide emulsion in the present invention and as a binder for other hydrophilic colloid layers, but other hydrophilic colloids may also be used. You can

Examples of the hydrophilic colloid include proteins such as gelatin derivatives, graft polymers of gelatin and other polymers, albumin, casein; cellulose derivatives,
For example, hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates; sugar derivatives, for example, sodium alginate, starch derivatives; various synthetic hydrophilic polymer substances such as single or copolymers, for example polyvinyl alcohol, polyvinyl alcohol partial acetal, poly -N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole can be used.

Examples of the gelatin include lime-processed gelatin, acid-processed gelatin and Bull. Soc. Sci. P
photo. Japan. No. 16. P30 (196
The enzyme-treated gelatin as described in 6) may be used, or a hydrolyzed product or an enzymatically decomposed product of gelatin can also be used.

Further, it is particularly preferable in the present invention to use a low molecular weight gelatin having a molecular weight of 70,000 or less at the time of nucleation.

On the other hand, the silver halide color photographic light-sensitive material of the present invention comprises at least one of a blue-sensitive layer, a green-sensitive layer and a red-sensitive silver halide emulsion layer on a support, and A non-photosensitive layer may be provided if necessary, and the emulsion layer contains a silver halide emulsion prepared as described above. There are no particular restrictions on the number and order of layers of the silver halide emulsion layer and the non-photosensitive layer. As a typical example, at least one photosensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities is typically provided on a support.
And a light-sensitive layer is a unit light-sensitive layer having color sensitivity to any of blue light, green light, and red light. In general, the unit photosensitive layers are arranged in order of the red-sensitive layer, the green-sensitive layer and the blue-sensitive layer from the support side. 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.

A non-photosensitive layer such as an intermediate layer of each layer may be provided between the above-described silver halide photosensitive layers and as the uppermost layer and the lowermost layer.

The intermediate layer may be formed, for example, in JP-A-61-437.
No. 48, No. 59-113438, No. 59-11344.
No. 0, No. 61-20037, No. 61-20038 and the DIR compound may be contained, and a color mixing inhibitor may be contained as is usually used.

The plural silver halide emulsion layers constituting each unit photosensitive layer are preferably composed of West German Patent 1,121,
A two-layer structure of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer can be used as described in 470 or British Patent No. 923,045. 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.
In addition, for example, JP-A-57-112751, JP-A-62-12751.
200350, 62-206541, 62-2
As described in No. 06543, a low-sensitivity emulsion layer may be provided on the side farther from the support, and a high-sensitivity emulsion layer may be provided on the side closer to the support.

Specific examples of the arrangement of these photosensitive layers include:
From the side farthest from the support, for example, low-sensitivity blue photosensitive layer (BL) / high-sensitivity blue photosensitive layer (BH) / high-sensitivity green photosensitive layer (GH) / low-sensitivity green photosensitive layer (GL) / High-sensitivity red photosensitive layer (RH) / low-sensitivity red photosensitive layer (RL), or BH / BL / GL / GH / RH / RL, or BH
The order of / BL / GH / GL / RL / RH is mentioned.

Further, as described in JP-B-55-34932, blue-sensitive layers / GH / RH / GL / RL may be arranged in this order from the side farthest from the support. JP-A-56-25738 and 62-63936.
It is also possible to arrange in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support, as described in the specification.

In addition, as described in JP-B-49-15495, the upper layer is a silver halide emulsion layer having the highest sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lower layer is a lower layer. An example is an arrangement in which a silver halide emulsion layer having a lower photosensitivity than that of the middle layer is arranged and the photosensitivity is gradually decreased toward the support, and three layers having different sensitivities are arranged. 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, in the above three-layer structure, 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 may be arranged in this order. . Also, in the case of four layers or more, the arrangement may be changed as described above.

In order to improve color reproducibility, US Pat. Nos. 4,663,271, 4,705,744, 4,707,436 and JP-A-62-160448 are used.
No. 63-89850, BL, G
It is preferable to dispose a main photosensitive layer such as L and RL and a donor layer (CL) having a multi-layer effect having different spectral sensitivity distributions adjacent to or in proximity to the main photosensitive layer.

As described above, various layer structures and arrangements can be selected according to the purpose of each photosensitive material.

The silver halide grains other than the tabular grains used in the present invention will be described below. A preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention contains about 30 mol% or less of silver iodide.
It is silver iodobromide, silver iodochloride, or silver iodochlorobromide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide.

The silver halide grains in the photographic emulsion have regular crystals such as cubes, octahedra and tetradecahedrons, grains having irregular crystal forms such as spheres and plates.
It may have a crystal defect such as a twin plane or a composite form thereof.

The grain size of silver halide may be fine grains of about 0.2 μm or less or large grains having a projected area diameter of up to about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion.

The silver halide photographic emulsions other than the tabular grain emulsions which can be used in the photographic light-sensitive material of the present invention are, for example, Research Disclosure (RD) N.
o. 17643 (December 1978), pp. 22-23,
"I. Emulsion preparation
ion and types) ”, and ibid. No. 18
716 (November 1979), p.648, ibid. Thirty
7105 (Nov. 1989), pages 863-865, and Graphide, "Physics and Chemistry of Photography," published by Paul Montel, P. Glafkides, Chemie et.
Phisique Photographique, P
aul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duff).
in, Photographic Emulsion
Chemistry (FocalPress, 196)
6)), "Production and coating of photographic emulsions" by Zelikmann et al., Published by Focal Press (VL Zelikman et.
al. , Making and Coating P
photographic Emulsion, Foca
l Press, 1964).

In the present invention, US Pat. No. 3,574,62
No. 8, 3,655,394 and British Patent Nos. 1,4.
The monodisperse emulsion described in No. 13,748 is also preferable.

Further, tabular grains having an aspect ratio of about 3 or more, which does not depend on the preparation method of the present invention, can be used in the present invention. Such tabular grains are described by Gatov, Photographic Science and Engineering (Gutoff, Photographic Science).
ce and Engineering), Volume 14,
248-257 (1970); U.S. Pat. No. 4,43.
4,226, 4,414,310, 4,43
It can be easily prepared by the method described in 3,048, 4,439,520 and British Patent 2,112,157.

The crystal structure of the silver halide grains used in the present invention may be uniform, may have different halogen compositions inside and outside, may have a layered structure, and may be epitaxial. Silver halides having different compositions may be bonded by bonding, or may be bonded with a compound other than silver halide such as silver rhodanide and lead oxide. Also, a mixture of particles having various crystal forms may be used.

The silver halide emulsion that can be used in the present invention is
It may be a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which the latent image is formed inside the grain, or a type having a latent image in both the surface and the inside, but it is a negative type emulsion. is necessary. Among the internal latent image types, JP-A-63-2
The core / shell type internal latent image type emulsion described in No. 64740 may be used. The method for preparing this core / shell type internal latent image type emulsion is described in JP-A-59-133542. The thickness of the silver halide grain shell of this emulsion varies depending on the form of development treatment, but is preferably 3 to 40 nm, and particularly preferably 5 to 20 nm.

The silver halide emulsion used in the present invention is
Usually, those which have been physically aged, chemically aged and spectrally sensitized are used. The additive used in such a process is R.I.
D. No. 17643, the same No. 18716 and N
o. No. 307105, and the relevant parts are summarized in the table below.

In the light-sensitive material of the present invention, as described above, the grain size, grain size distribution of the light-sensitive silver halide emulsion,
Two or more kinds of emulsions having different characteristics of at least one of halogen composition, 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 light-sensitive silver halide emulsion layer and / or the substantially light-insensitive hydrophilic colloid layer. A silver halide grain whose inside or surface is fogged means a silver halide grain (emulsion) that enables uniform (non-imagewise) development regardless of the unexposed area and exposed area of the light-sensitive material. Say that. A method for preparing a silver halide grain whose inside or surface is fogged is described in US Pat. No. 4,62,62.
6,498 and JP-A-59-214852.

The silver halide forming the inner core of the fogged core / shell type silver halide grain may have the same halogen composition as the outer silver halide or a different halogen composition. Good. 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 0.75 μm, particularly 0.05 to 0.
6 μm is preferable. The grain shape is not particularly limited and may be regular grains or polydisperse emulsion, but the grain size distribution is monodisperse (the weight of silver halide grains or at least 80% of the number of grains is an average). Those having a particle size within ± 30% of the particle size) are preferable.

In the present invention, it is preferable to use non-photosensitive fine grain silver halide. The non-photosensitive fine grain silver halide is a silver halide grain that 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 the fog is not fogged in advance. .

The non-photosensitive fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may optionally contain silver chloride and / or silver iodide. Preferred is one containing 0.5 to 10 mol% of silver iodide.

The non-photosensitive fine grain silver halide has an average grain size (average value of circle-equivalent diameters of projected areas) of 0.01 to
0.5 μm is preferable, and 0.02 to 2 μm is more preferable.

The non-photosensitive 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 non-photosensitive silver halide fine particles need not be optically sensitized and spectral sensitization is also unnecessary. 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, or mercapto-based compound or a zinc compound in advance. Colloidal silver can be preferably contained in the layer containing the fine silver halide grains.

The amount of silver coated on the light-sensitive material of the present invention was 6.0 g.
/ M ² or less is 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 described in the above three R.S. D. , And the relevant locations are shown in the table below.

Types of additives RD17643 RD18716 RD307105 1. Chemical sensitizer Page 23 Page 648 Right column Page 866 2. Sensitivity enhancer Page 648, right column 3. Spectral sensitizer, pages 23 to 24, page 648, right column to pages 866 to 868, supersensitizer, page 649, right column 4. Whitening agent Page 24 Page 647 Right column Page 868 5. Antifoggant 24 to 25 pages 649 right column 868 to 870 Stabilizer 6. Light absorber, pages 25 to 26, page 649, right column to page 873, filter dye, page 650, left column, ultraviolet absorber 7. Anti-staining agent, page 25, right column, page 650, left column to page 872, right column 8. Dye image stabilizer page 25 page 650 page left column page 872 9. Hardener 26 pages 651 pages left column 874-875 pages 10. Binder page 26 page 651 left column 873 to page 874 11. Plasticizers, lubricants Page 27 Page 650 Right column Page 876 12. Coating aid, pages 26 to 27, page 650, right column, pages 875 to 876, surfactant 13. Antistatic agent Page 27 Page 650 Right column 876-877 Page 14. Matting agent pp. 878-879 Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, it is immobilized by reacting with formaldehyde described in US Pat. Nos. 4,411,987 and 4,435,503. It is preferable to add a compound capable of being added to the light-sensitive material.

The light-sensitive material of the present invention includes US Pat.
40,454, 4,788,132, JP-A-6
It is preferable to incorporate the mercapto compounds described in JP-A No. 2-18539 and JP-A No. 1-283551.

The light-sensitive material of the present invention is described in JP-A-1-106.
No. 052, it is preferable to add a compound which releases a fog, a development accelerator, a silver halide solvent or a precursor thereof regardless of the amount of developed silver produced by the development processing.

For the light-sensitive material of the present invention, the international publication WO88 is used.
No. 04794, Dyes dispersed by the method described in JP-A-1-502912, or EP317, 308A
U.S. Pat. No. 4,420,555, JP-A-1-259.
It is preferable to incorporate the dye described in No. 358.

Various color couplers can be used in the light-sensitive material of the present invention. A specific example is the R.
D. No. 17643, VII-CG, and No. 17643.
307105, VII-C to G.

Examples of yellow couplers include US Pat. Nos. 3,933,501 and 4,022,620.
Issue No. 4,326,024, No. 4,401,75
No. 2, No. 4,248,961, Japanese Patent Publication No. 58-107.
39, British Patent Nos. 1,425,020 and 1,4
76,760, U.S. Pat. Nos. 3,973,968, 4,314,023, 4,511,649,
The compounds described in EP 249,473A are preferred.

Examples of magenta couplers include 5-
Pyrazolone-based and pyrazoloazole-based compounds are used. For example, US Pat. Nos. 4,310,619, 4,351,897, EP 73,636, and US Pat. No. 3,061,432 are used. Issue No. 3,725,06
No. 7, R.I. D. No. 24220 (June 1984),
JP-A-60-33552, R.I. D. No. 24230
(June 1984), JP-A-60-43659, 6
1-72238, 60-35730, 55-1
No. 18034, No. 60-185951, U.S. Patent Nos. 4,500,630, 4,540,654, 4,556,630, and International Publication WO88 / 0479.
The compounds described in No. 5 are particularly preferable.

As the silane coupler, phenol-based and naphthol-based couplers are used. Examples thereof include US Pat. Nos. 4,052,212 and 4,146,396.
No. 4,228,233, No. 4,296,200
No. 2, No. 2,369,929, No. 2,801,17
No. 1, No. 2,772, 162, No. 2,895, 8
No. 26, No. 3,772,002, No. 3,758,
No. 308, No. 4,334, 011 and No. 4,32
7,173, West German Patent Publication No. 3,329,729,
European Patent Nos. 121,365A and 249,453A
U.S. Pat. Nos. 3,446,622 and 4,33.
No. 3,999, No. 4,775,616, No. 4,4
No. 51,559, No. 4,427,767, No. 4,
Those described in 690,889, 4,254,212, 4,296,199, and JP-A-61-42658 are preferable. Furthermore, JP-A-64-553,
No. 64-554, No. 64-555, and No. 64-556.
The pyrazoloazole-based couplers described in U.S. Pat. No. 4,849,639 and the imidazole-based couplers described in U.S. Pat. No. 4,818,672 can also be used.

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.
No.

Examples of the coupler in which the color forming dye has an appropriate diffusibility include US Pat. No. 4,366,237, US Pat. No. 2,125,570, European Patent 96,570, and US Pat.
The compounds described in West German Patent (Publication) No. 3,234,533 are preferable.

As the colored coupler for correcting the unnecessary absorption of the coloring dye, R.I. D. No. 17643
No. VII-G, the same No. Item VII-G of 307105, U.S. Pat. No. 4,163,670, Japanese Patent Publication No. 57-39413.
U.S. Pat. Nos. 4,004,929 and 4,13.
The compounds described in 8,258 and British Patent 1,146,368 are preferred. Also, U.S. Pat. No. 4,774,1
No. 81, a coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released upon coupling, and a dye precursor capable of reacting with a developing agent described in US Pat. No. 4,777,120 to form a dye. It is also preferable to use a coupler having a group as a leaving group.

In the light-sensitive material of the present invention, compounds which release a photographically useful residue upon coupling can also be preferably used. Examples of the DIR coupler which releases a development inhibitor include RD17643, VII-F and N.
o. 307105, Patents described in Section VII-F, JP-A Nos. 57-151944, 57-154234, 60-184248, 63-37346, and 63.
The compounds described in -37350, U.S. Pat. Nos. 4,248,962 and 4,782,012 are preferred.

For example, R.I. D. No. 11449 and 2
The bleaching accelerator-releasing couplers described in JP-A No. 4241 and JP-A No. 61-201247 are effective for shortening the processing time having a bleaching ability, and particularly, the light-sensitive material using the tabular silver halide grains described above. The effect is great when added to. As a coupler which releases a nucleating agent or a development accelerator imagewise during development, British Patent No. 2,092
7,140, 2,131,188, JP-A-59
The compounds described in Nos. 157638 and 59-170840 are preferable. Further, JP-A-60-107029,
By a redox reaction with an oxidation product of a developing agent described in JP-A-60-252340, JP-A-1-44940 and JP-A-1-45687, for example, a fogging agent, a development accelerator and a silver halide solvent are released. Compounds are also preferred.

Other compounds that can be used in the light-sensitive material of the present invention include, for example, US Pat. No. 4,13.
Competitive couplers described in 0,427, for example, U.S. Pat. Nos. 4,283,472, 4,338,393,
Multiequivalent couplers described in JP-A No. 4,310,618, for example, JP-A-60-185950 and JP-A-62-24.
No. 252, DIR redox compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing redox compound or DIR redox releasing redox compound, European Patent Nos. 173,302A, 31
No. 3,308A, a coupler that releases a dye that recolors after being released, for example, a ligand-releasing coupler described in US Pat. No. 4,555,477, JP-A-63-75747.
And the couplers releasing a fluorescent dye described in US Pat. No. 4,774,181.

In the present invention, the coupler can be introduced into the light-sensitive material by various known dispersion methods. As an example,
Examples include an oil-in-water dispersion method and a latex dispersion method.

Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in, for example, US Pat. No. 2,322,027. Specific examples of the high-boiling organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include phthalic acid esters (for example, dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate). , Bis (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl) isophthalate, bis (1,1)
-Diethylpropyl) phthalate), esters of phosphoric acid or phosphonic acid (eg triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxy) Ethyl phosphate,
Trichloropropyl phosphate, di-2-ethylhexylphenyl phosphonate), benzoic acid esters (for example, 2-ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl-p-hydroxybenzoate), amides (for example, 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-tert-octylaniline) and hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene). Moreover, as an auxiliary solvent,
For example, an organic solvent having a boiling point of about 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, and 2-ethoxyethyl acetate. And dimethylformamide.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,19.
No. 9,363, West German Patent Application (OLS) No. 2,541,
274 and 2,541,230.

In the color light-sensitive material of the present invention, for example,
Phenethyl alcohol and JP-A-63-257747,
No. 62-272248, and JP-A-1-80941.
1,2-benzisothiazolin-3-one described in No.
Add various preservatives or mildewcides such as n-butyl-p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol, 2- (4-thiazolyl) benzimidazole. Is preferred.

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

Suitable supports which can be used in the light-sensitive material of the present invention are described in, for example, R. D. No. 28 of 17643
Page, ibid. No. 18716, page 647, right column to page 648, left column, and ibid. 307105, page 879.

In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is 28 μm.
It is preferably at most 23 μm, more preferably at most 18 μm, still more preferably at most 16 μm
The following are particularly preferred. The film swelling rate T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. Here, the film thickness means the 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 (A. Gr
een) and others in Photographic Science and Engineering (Photogr. Sci. E.
ng. ), Vol. 19, No. 2, was measured by using a type of Swellometer described (swelling meter) pp 124-129, T _1/2 is 30 ° C. The light-sensitive material with a color developing solution, 3 minutes 90% of the maximum swollen film thickness reached after processing for 15 seconds is defined as the saturated film thickness, which is defined as the time until it reaches 1/2 of the saturated film thickness of the photosensitive material.

The film swelling speed T _1/2 can be adjusted by adding a film hardening agent to gelatin as a binder or by changing the aging condition after coating. The swelling rate is preferably 150 to 400%. Here, 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. The back layer preferably contains, for example, the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, and surface active agent. .. The swelling ratio of this back layer is preferably 150 to 500%.

The photographic light-sensitive material according to the present invention can be produced by the method described in R. D. No. 17643, pages 28-29, ibid. 1
8716, 651 left column to right column, and the same No. 3071
Development can be carried out by a usual method described on page 880-881 of No. 05.

The color developing solution used in 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. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used. Typical examples thereof include 3-methyl-4-amino-N, N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N. -Ethyl-N-β-methanesulfonamide ethylaniline, 3-methyl-4-
Amino-N-ethyl-β-methoxyethylaniline and their sulphates, hydrochlorides or p-toluenesulphonates. Among these, especially 3-methyl-
4-Amino-N-ethyl-N-β-hydroxyethylaniline sulfate is preferred. Two or more of these compounds can be used in combination depending on the purpose.

The color developer contains a pH buffering agent such as an alkali metal carbonate, borate or phosphate, a chloride salt, a bromide salt, an iodide salt, a benzimidazole,
It is common to include a development inhibitor such as benzothiazoles or mercapto compounds, or an antifoggant. Further, the color developing solution, if necessary, hydroxylamine, diethylhydroxylamine, sulfite,
Hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, various preservatives such as triethanolamine and catecholsulfonic acid, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium Development accelerators such as salts and amines, dye-forming couplers, competitive couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, tackifiers, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, Various chelating agents represented by phosphonocarboxylic acid, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylide. -1,1-Diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof May be included.

When the reversal process is performed on the light-sensitive material of the present invention, black-and-white development is usually performed and then color development is performed. The black-and-white developer includes, for example, dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol. These known black-and-white developing agents can be used alone or in combination.

PH of these color developing solution and black and white developing solution
Is generally 9 to 12. The replenishing 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, and 500 ml can be obtained by reducing the bromide ion concentration in the replenishing solution. It can also be:
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 the air in the processing tank can be expressed by the aperture ratio defined below. Aperture ratio = [contact area between treatment liquid and air (cm ² )] ÷
[Volume of Treatment Liquid (cm ³ )] The aperture ratio is preferably 0.1 or less, and more preferably 0.001 to 0.05. As a means for reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the surface of the photographic processing liquid in the processing tank, Japanese Patent Laid-Open No.
The method using a movable lid described in 82033 and the slit development processing method described in JP-A-63-216050 can be mentioned. The means to reduce the aperture ratio is
It is preferable to apply not only to both the color development and the black and white development but also to the subsequent steps, for example, all the steps such as bleaching, bleach-fixing, fixing, washing and stabilizing. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution.

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

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. To further speed up the process, a bleach-fixing process may be performed after the bleaching process. 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 according to the purpose. As the bleaching agent, for example, polyvalent metal compounds such as iron (III), peracids, quinones, and nitro compounds are used. Typical bleaching agents include organic complex salts of iron (III) such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid and glycol etherdiaminetetraacetic acid. Examples thereof include aminopolycarboxylic acids or complex salts such as citric acid, tartaric acid and malic acid. Of these, iron (III) aminopolycarboxylates including ethylenediaminetetraacetic acid iron (III) complex salts and 1,3-diaminopropanetetraacetic acid iron (III) complex salts
Complex salts are preferable from the viewpoint of rapid processing and prevention of environmental pollution. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution. The pH of a bleaching solution or a bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 4.0 to 8, but a lower pH can be used for speeding up the processing.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath.
Specific examples of useful bleaching accelerators include US Pat.
93,858, West German Patents 1,290,812, 2,059,988, JP-A-53-32736, 53-57831, 53-37418, 53-.
No. 72623, No. 53-95630, No. 53-956
No. 31, No. 53-104232, No. 53-12442
No. 4, No. 53-141623, No. 53-28426.
No., R. D. No. 17129 (July 1978), a compound having a mercapto group or a disulfide group; a thiazolidine derivative described in JP-A-50-140129; JP-B-45-8506, JP-A-52-208.
32, 53-32735, U.S. Pat. No. 3,70.
Thiourea derivatives described in 6,561; West German Patent No. 1,
127,715, iodide salts described in JP-A-58-16,235; West German Patent Nos. 966,410, and 2,74.
No. 8,430, polyoxyethylene compounds; Japanese Patent Publication No. 45-8836, polyamine compounds; Others, JP-A-49-40, 943 and 49-59, 644.
No. 53-94, 927, 54-35, 727.
No. 55, No. 55-26, 506, No. 58-163, 940.
Compounds described in No. 1; bromide ions. Of these, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large accelerating effect, and particularly, US Pat. No. 3,893,858 and West German Patent 1,290,81.
No. 2, and the compounds described in JP-A No. 53-95,630 are preferable. 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.

In addition to the above compounds, the bleaching agent and the bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach stain. A particularly preferred organic acid is a compound having an acid dissociation constant (pKa) of 2 to 5, specifically acetic acid,
Propionic acid and hydroxyacetic acid are preferred.

Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodide salts. Of these, the use of thiosulfates is common, with ammonium thiosulfate being the most widely used. Further, it is also preferable to use thiosulfate in combination with a thiocyanate, a thioether compound, or a compound such as thiourea. As a preservative for fixers and bleach-fixers,
Preferred are sulfites, bisulfites, carbonyl bisulfite adducts or sulfinic acid compounds described in EP 294769A. Further, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution and the bleach-fixing solution for the purpose of stabilizing the solution.

In the present invention, a compound having a pKa of 6.0 to 9.0 for adjusting the pH, preferably imidazole, 1-methylimidazole, 1-ethylimidazole or 2-, is added to the fixer or the bleach-fixer. It is preferable to add 0.1 to 10 mol / liter of an imidazole such as methylimidazole.

The total time of the desilvering step in the development processing is preferably short as long as no desilvering failure occurs. The preferred time is 1 to 3 minutes, more preferably 1 to 2 minutes. The treatment temperature is 25 ° C to 50 ° C, preferably 35 ° C.
C to 45C. In the preferable temperature range, the desilvering rate is improved, and the stain generation after the processing can be effectively prevented.

In the desilvering process, it is preferable that the stirring is strengthened as much as possible. As a specific method for strengthening stirring, for example, a method of causing a jet stream of a processing solution to collide with an emulsion surface of a light-sensitive material described in JP-A-62-183460 or a rotating means of JP-A-62-183461 is used. To improve the stirring effect, and further to move the photosensitive material while bringing the emulsion surface into contact with the wiper blade provided in the solution to further improve the stirring effect by making the emulsion surface turbulent. There is a method of increasing the total circulation flow rate. Such a method of enhancing stirring is effective in any of a bleaching solution, a bleach-fixing solution and a fixing solution. It is considered that the strengthening of stirring accelerates the supply of the bleaching agent and the fixing agent into the emulsion film, and consequently increases the desilvering rate. Further, the agitation and strengthening method described above 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 development processing of the light-sensitive material of the present invention is disclosed in JP-A-60-191257 and 60-60.
It is preferable to provide the photosensitive material transporting means described in JP-A-191258 and JP-A-60-191259. As described in JP-A-60-191257, such a conveying means can significantly reduce the carry-in of the treatment liquid from the front bath to the rear bath, and has a high effect of preventing the deterioration of the performance 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 silver halide color photographic light-sensitive material according to the present invention is generally subjected to washing and / or stabilizing steps after desilvering. The amount of rinsing water in the rinsing step is the characteristics of the photosensitive material (for example, depending on the material used such as a coupler), application, and further, the rinsing water temperature, the number of rinsing tanks (the number of stages), for example, a replenishing method such as countercurrent or forward flow, It can be set in a wide range according to various other conditions. Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent system is
of the Society of Motion
Picture and Television E
nginesers, vol. 64, p. 248-253 (1
May 955 issue).
According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be significantly reduced, but, for example, bacteria are propagated due to an increase in the residence time of water in the tank, and the produced suspended matter adheres to the photosensitive material. Such a problem occurs. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method of reducing calcium ion and magnesium ion described in JP-A-62-288838 can be used very effectively. Moreover, for example, isothiazolone compounds and siabendazoles described in JP-A-57-8,542, chlorine-based germicides such as chlorinated sodium isocyanurate, and other benzotriazoles, such as those described by Hiroshi Horiguchi, "Prevention Chemistry of antifungal agents "(1986
Year) Sankyo Publishing, Sanitary Technology Society, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982) Industrial Technology Association, Japan Antibacterial and Antifungal Society, "Encyclopedia of Antibacterial and Antifungal Agents" (1986) It is also possible to use the bactericide of.

The pH of washing water in the processing of the light-sensitive material of the present invention is 4-9, preferably 5-8. The washing water temperature and the washing time can be set variously depending on the characteristics and use of the light-sensitive material, but generally, they are selected at 15 to 45 ° C. for 20 seconds to 10 minutes, preferably at 25 to 40 ° C. for 30 seconds to 5 minutes. To be done. 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 stabilizing treatment, JP-A-57-8543 and 58-58
All known methods described in Nos. 14834 and 60-220345 can be applied.

In some cases, the washing treatment is further followed by a stabilizing treatment. As an example of the stabilizing treatment, a stabilizer containing a dye stabilizer and a surfactant used as a final bath of a color light-sensitive material for photographing is used. Treatment with a bath can be mentioned. Examples of dye stabilizers include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts. Various chelating agents and antifungal agents can also be added to this stabilizing bath.

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

In the processing using an automatic processor, when each processing solution described above is concentrated by evaporation, it is preferable to add water to correct the concentration.

The photographic light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, US Pat. No. 3,342,59
Indoaniline compounds described in No. 7, No. 3,342,
599, R.I. D. No. 14, 850 and the same No. 1
Schiff base type compound described in US Pat.
Aldol compounds described in US Pat. No. 3,719,
Metal salt complexes described in Japanese Patent No. 492, JP-A-53-13562
The urethane compound described in No. 8 can be mentioned.

The photographic light-sensitive material of the present invention, if necessary,
For the purpose of accelerating color development, various 1-phenyl-3-
You may incorporate pyrazolidones. A typical compound is
For example, JP-A-56-64339 and JP-A-57-1445.
47 and 58-115438.

For the light-sensitive material of the present invention, various processing solutions are
Used at 0 ° C to 50 ° C. Normally 33 ° C-38
Although the temperature of ℃ is standard, it can be set to a higher temperature to accelerate the processing to shorten the processing time, and conversely, to set a lower temperature to improve the image quality and the stability of the processing liquid. it can.

The photographic light-sensitive material of the present invention is, for example,
U.S. Pat. No. 4,500,626, JP-A-60-133
No. 449, No. 59-218443, No. 61-2380.
No. 56 and European Patent No. 210,660A2 can be applied to the photothermographic material.

The photographic light-sensitive material of the present invention is disclosed in JP-B-2-32.
When applied to the film unit with a lens described in No. 615 and Japanese Utility Model Publication No. 3-39784, the effect is more easily exhibited and it is effective.

[0211]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited thereto. Example 1 (Preparation of seed crystal emulsion Em-1) An aqueous solution prepared by dissolving 6 g of an inert low molecular weight (average molecular weight of 50,000) gelatin and 2.5 g of potassium bromide in 1 liter of distilled water was stirred at 30 ° C.
A 1 M aqueous solution of silver nitrate and a 1 M aqueous solution of potassium bromide and potassium iodide (molar ratio: 92/8) were added thereto at a flow rate of 50 cc / min for 40 seconds. Then pAg
Was adjusted to 8.5, 20 g of inert gelatin was added, and 6
After the temperature was raised to 5 ° C., 50 g of ammonium nitrate and 100 cc of 1 M aqueous sodium hydroxide solution were added and aged for 30 minutes to form a plate nucleus. Furthermore, after adding 8 g of glacial acetic acid, 100 cc of a 1M aqueous solution of silver nitrate and 1 part of potassium bromide were added.
An aqueous solution of M was added in equimolar amounts at an addition rate near the critical growth rate to form shells, thereby growing tabular silver bromide grains to obtain emulsion Em-1. At this time, the silver potential was kept at +10 mV against the saturated calomel electrode. A total of 135 g of silver nitrate was used for grain growth.

The resulting emulsion Em-1 was desalted by a usual flocculation method, gelatin was added thereto, and p was added.
It was adjusted to H6.0 and pAg8.5 and stored in a refrigerator.

Em-1 is an emulsion in which grains having an aspect ratio of 3.0 or more are present in 92% of the projected area of all silver halide grains in the emulsion, and are tabular grains having an equivalent spherical diameter of 0.18 μm and a variation coefficient of 27%. It was an emulsion composed of granular particles. (Preparation of seed crystal emulsions Em-2 to Em-10) Em described above
-1 in the production method of compound -1, immediately before the start of shell formation
-2, or Compound I-16 was added at the addition amount shown in Table 1 below to form grains, and emulsions of Em-2 to 7 were obtained.

In the method for producing Em-1, just before the start of grain formation, compound I-16 was added in the addition amount shown in Table 1 to form grains, whereby Em-8 was obtained.

In the method for producing Em-1, Compound I-16 was added at the addition amount shown in Table 1 at the time of gelatin addition after the desalting step to obtain Em-9.

In the process for producing Em-1, the compound I-was added immediately before the start of shell formation and when gelatin was added after the desalting step.
16 was added in the addition amount shown in Table 1 to form particles, thereby obtaining Em-10. (Preparation of seed crystal emulsions Em-11 to Em-12) In the process for producing Em-1, by changing the silver potential at the time of shelling to +40 mV, grains having an aspect ratio of 2.0 or more are completely halogenated in the emulsion. Em-11 consisting of tabular grains having a sphere-equivalent diameter of 0.18 μm and a coefficient of variation of 19%, which was present in 5% of the projected area of silver grains, was prepared.

In the process for preparing Em-11, Compound I-16 was added at the addition amount shown in Table 1 just before the start of shell formation, and particles were formed to obtain Em-12.

[0218]

[Table 1] (Preparation of Em-1-1) 20 g of deionized gelatin, and Em-1 stored as a seed crystal emulsion and refrigerated for 1 day
1350 ml of an aqueous solution containing 0.03 mol of silver at 75 ° C
And the pH was adjusted to 5.5. Next, an aqueous solution of silver nitrate (115 g of AgNO ₃ ) and an aqueous solution of halogen (KI to KB
Seed crystal grains were grown at an addition rate close to critical growth by adding (accelerating 2.0 mol% to r) with a double jet to accelerate the flow rate for 32 minutes. At this time, the silver potential was kept at -25 mV against the saturated calomel electrode.
Here, after adding an aqueous solution containing 8.0 g of potassium iodide, an aqueous silver nitrate solution (53 g of AgNO ₃ ) and an aqueous potassium bromide solution (KBr 37 g) were added by a double jet.
The resulting emulsion is desalted by the usual flocculation method,
After adding gelatin, the pH was adjusted to 5.5 and pAg 8.8 to obtain an emulsion Em-1-1. Em-1-1 is an emulsion in which grains having an aspect ratio of 4.0 or more are present in an amount of 86% of the projected area of all silver halide grains in the emulsion, and the equivalent spherical diameter is 0.78 µ, and the variation coefficient is 22%. The emulsion consisted of tabular grains. (Preparation of Em-1-2, Em-1-3) In the method for producing Em-1-1, the emulsion Em-1- was prepared by using Em-1 as a seed crystal emulsion, which was stored in the refrigerator for 90 days. Got 2.

In the process for preparing Em-1-1, an emulsion Em-1-3 was prepared by using Em-1 which was prepared as a seed crystal emulsion, which was stored in the refrigerator for 1 day and then dissolved at 75 ° C. for 8 hours. .

The grains in the emulsion thus obtained were the same as Em-1-1. (Em-2-1 to Em-10-1, Em-2-2 to Em
Preparation of -10-2, Em-2-3 to Em-10-3) E
In the production method of m-1-1, Em-2 is used as a seed crystal emulsion.
To Em-10 and emulsions Em-2-1 to Em
-10-1 was prepared.

In the process for preparing Em-1-2, Em-2 to Em-10 were used as seed crystal emulsions to prepare emulsion Em-2.
-2 to Em-10-2 were prepared.

In the process for preparing Em-1-3, Em-2 to Em-10 were used as seed crystal emulsions to prepare emulsion Em-2.
-3 to Em-10-3 were prepared.

The grains in the emulsion thus obtained were the same as Em-1-1. (Preparation of Em-11-1, Em-11-1) Em-1-
In the production method of 1, the emulsions Em-11-1 to Em- using Em-11 to Em-12 as seed crystal emulsions.
12-1 was prepared. However, the silver potential during grain growth is -4
It was kept at 0 mV. Em-11-1 and Em-12-1
Is an emulsion in which grains having an aspect ratio of 4.0 or more are present at 71% of the projected area of all silver halide grains in the emulsion,
The tabular grains had a sphere-equivalent diameter of 0.78 μm and a coefficient of variation of 32%. (Preparation of Em-11-2-3, Em-12-2-3) E
In the production method of m-1-2, Em-1 is used as a seed crystal emulsion.
Emulsions Em-11-2 to Em-12-2 were prepared using 1 to Em-12. However, the silver potential during grain growth was kept at -40 mV.

In the process for preparing Em-1-3, Em-11 to Em-12 were used as seed crystal emulsions to prepare emulsion Em-.
11-3 to Em-12-3 were prepared. However, the silver potential during grain growth was kept at -40 mV.

The grains in the emulsion thus obtained were the same as Em-11-1.

For each emulsion prepared as described above,
Gold and sulfur sensitization was performed as follows. The temperature of each emulsion was raised to 60 ° C., and the following sensitizing dye A was added at 6.8 × 10 ⁻⁴ mol / mol A.
g, similarly 1.2 × 10 ⁻⁴ mol / mol Ag of antifoggant A, 8.5 × 10 ⁻⁶ mol / mol A of sodium thiosulfate
g, chloroauric acid 1.7 × 10 ⁻⁵ mol / mol Ag and potassium thiocyanate 1.2 × 10 ⁻³ mol / mol Ag, N,
N-dimethylselenourea 0.5 × 10 ^-5 mol / mol Ag
Was sequentially added for optimal chemical sensitization. here,
“Optimum chemical sensitization” means 1/10 after chemical sensitization
It refers to chemical sensitization that maximizes the sensitivity when exposed for 0 seconds.

A coating sample was prepared by sequentially providing each layer of the following formulation on the triacetyl cellulose support from the support side. Samples 101 to 136 were prepared using the emulsion having the above-mentioned chemical sensitization in the emulsion layer. (1) Emulsion layer ・ Emulsion ... Various emulsions (silver 2.4 × 10 ^-2 mol / m ² ) -Coupler (1.2 × 10 ^-3 mol / m ² ) -Tricresyl phosphate (1) .10 g / m ² ) ・ Gelatin (2.30 g / m ² ) (2) Protective layer ・ 2,4-Dichloro-6-hydroxy-S-triazine sodium salt (0.08 g / m ² ) ・ Gelatin (1. 80 g / m ² )

[0228]

[Chemical 17] These samples 101 to 136 are placed at 40 ° C. and a relative humidity of 70.
% Of the sample was left for 14 hours, and a part of each sample was immediately stored, and a part of the sample was stored in an atmosphere of 40 ° C. and 40% RH for 30 days, and then a gelatin filter SC50 manufactured by Fuji Photo Film Co., Ltd. and a continuous wedge. And exposed for 1/100 seconds to carry out the following color development processing.

Further, the treated sample was concentrated and measured with a green filter.

Step Processing time Processing temperature Color development 2 minutes 00 seconds 40 ° C. Bleach fixing 3 minutes 00 seconds 40 ° C. Water washing (1) 20 seconds 35 ° C. Water washing (2) 20 seconds 35 ° C. Stability 20 seconds 35 ° C. Dry dry 50 seconds 65 ° C. Next, the composition of each processing solution used is described. (Color developer) (Unit: g) Diethylenetriaminepentaacetic acid 2.0 1-Hydroxyethylidene-1,1-diphosphonic acid 3.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1. 5 mg Hydroxylamine sulfate 2.4 4- [N-ethyl-N-β-hydroxyethyl 4.5 amino] -2-methylaniline sulfate Add water 1.0 liter pH 10.05 (bleach-fixer) (Unit: g) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 90.0 Ethylenediaminetetraacetic acid disodium salt 5.0 Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution (70%) 260.0 ml Acetic acid (98%) 5.0 ml Bleach accelerator 0.01 mol

[0231]

[Chemical 18] 1.0 liter pH 6.0 (water washing liquid) was added water, and tap water was used as an H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas).
And OH type anion exchange resin (the same Amberlite IR-
400) and water are passed through a mixed-bed column to reduce the concentration of calcium and magnesium ions to 3 mg / liter or less, and then this solution is treated with 20 mg / liter of sodium diisocyanurate dichloride and 1.5 g of sodium sulfate.
Was added to obtain a water washing solution.

The pH of this liquid is in the range of 6.5-7.5. (Stabilizing liquid) (Unit: g) Formalin (37%) 2.0 ml Polyoxyethylene-p-monononiphenyl ether 0.3 (Average degree of polymerization 10) Ethylenediaminetetraacetic acid disodium salt 0.05 Water was added 1. 0 liter pH 5.0-8.0 The sensitivity of each sample was determined as the relative value of the reciprocal of the exposure amount expressed in lux · sec which gives a density of 0.2 on the fog.
Regarding the sensitivity, the relative value with the sensitivity of the sample 101 being 100 and the relative value with the sensitivity of the sample (Em number ending with -1) using the seed crystal emulsion which has not been aged as 100 are shown together. It was

The results of each evaluation relating to Samples 101 to 136 are shown in Tables 2 and 3 below.

[0234]

[Table 2]

[0235]

[Table 3] From the results shown in Tables 2 and 3, the emulsion preparation method according to the present invention has extremely small performance fluctuation due to the storage conditions of the seed emulsion.
It was also found that a tabular emulsion having high sensitivity and improved storability can be obtained. Example 2 An emulsion was prepared by multiplying the preparation scale by 70 times and 490 times in the production method of Em-1-1 of Example 1. The obtained emulsions were Em-101-1 and Em-201, respectively.
-1. These emulsions used equipment that was similar magnified 70 times and 490 times (and therefore 4.12 times and 7.88 times in the length dimension, respectively) to the preparation equipment used in Example 1.

Further, the Em-10-1 of Example 1 was also scaled up in the same manner as described above to obtain Em-110-1.
And Em-210-1 were obtained.

The above emulsions were subjected to gold-sulfur sensitization in the same manner as in Example 1 to prepare samples 201 to 204.

These samples were evaluated in the same manner as in Example 1 and the results shown in Table 4 below were obtained.

[0239]

[Table 4] From the results shown in Table 4, it was found that the emulsion preparation method according to the present invention can provide a tabular emulsion having a small scale-up dependence. Example 3 On a subbed cellulose triacetate film support,
Each layer having the composition shown below was applied in multiple layers to prepare a sample 301 which is a multilayer color light-sensitive material. (Photosensitive layer composition) The main materials used for each layer are classified as follows: ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling point organic solvent ExY: Yellow coupler H: Gelatin Curing agent ExS: Sensitizing dye The numbers corresponding to the respective components indicate the coating amount expressed in g / m ² , and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer. (Sample 301) First layer (antihalation layer) Black colloidal silver Silver 0.18 Gelatin 1.40 ExM-1 0.18 ExF-1 2.0 × 10 ^-3 HBS-1 0.20 Second layer (intermediate) Layer) Silver iodobromide emulsion G Silver 0.065 2,5-di-t-pentadecylhydroquinone 0.18 ExC-2 0.020 UV-1 0.060 UV-2 0.080 UV-3 0.10. HBS-1 0.10 HBS-2 0.020 Gelatin 1.04 Third layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion A silver 0.30 Silver iodobromide emulsion B silver 0.30 ExS-1 7.2 × 10 ⁻⁵ ExS-2 2.2 × 10 ⁻⁵ ExS-3 3.5 × 10 ⁻⁴ ExC-1 0.17 ExC-3 0.030 ExC-4 0.10 ExC-5 0. 020 ExC-7 0.0050 ExC-8 0.010 Cpd 2 0.025 HBS-1 0.10 Gelatin 0.87 Fourth Layer (medium-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion D silver ^{0.68 ExS-1 3.5 × 10 -4} ExS-2 2. 0 × 10 ⁻⁵ ExS-3 5.1 × 10 ⁻⁴ ExC-1 0.13 ExC-2 0.060 ExC-3 0.0070 ExC-4 0.090 ExC-5 0.025 ExC-7 0. 0010 ExC-8 0.0070 Cpd-2 0.023 HBS-1 0.10 Gelatin 0.75 Fifth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion Em301 Silver 1.75 ExS-1 2.2 × 10 ^-4 ExS-2 1.3 × 10 ^-4 ExS-3 2.8 × 10 ^-4 ExC-1 0.18 ExC-3 0.045 ExC-6 0.020 ExC-8 0.025 Cpd- 2 0.050 HBS-1 0.20 HBS-2 0.10 Gelatin 1.15 Sixth layer (intermediate layer) Cpd-1 0.10 HBS-1 0.50 Gelatin 1.10 Seventh layer (low sensitivity green sensitive emulsion layer) Silver iodobromide emulsion C Silver 0.35 ExS- 4 3.0 × 10 ^-5 ExS-5 2.1 × 10 ^-4 ExS-6 8.0 × 10 ^-4 ExM-1 0.010 ExM-2 0.33 ExM-3 0.086 ExY-10 .015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.73 Eighth layer (medium sensitivity green sensitive emulsion layer) Silver iodobromide emulsion D Silver 0.80 ExS-4 3.2 × 10 ^-5 ExS -5 2.2 x 10 ^-4 ExS-6 8.4 x 10 ^-4 ExM-2 0.13 ExM-3 0.030 ExY-1 0.018 HBS-1 0.16 HBS-3 8.0x 10 ^-3 gelatin 0.90 9th layer (high-sensitivity green-sensitive emulsion layer) silver iodobromide emulsion E silver 1.45 ExS -4 3.7 x 10 ^-5 ExS-5 8.1 x 10 ^-5 ExS-6 3.2 x 10 ^-4 ExC-1 0.010 ExM-1 0.030 ExM-4 0.040 ExM-5 0.019 Cpd-3 0.040 HBS-1 0.25 HBS-2 0.10 Gelatin 1.44 10th layer (yellow filter layer) Yellow colloidal silver 0.030 Cpd-1 0.16 HBS-10 .60 gelatin 0.60 11th layer (low-sensitivity blue-sensitive emulsion layer) silver iodobromide emulsion C silver 0.18 ExS-7 8.6 × 10 ⁻⁴ ExY-1 0.020 ExY-2 0.22 ExY -3 0.50 ExY-4 0.020 HBS-1 0.28 Gelatin 1.10 12th layer (medium-sensitive blue-sensitive emulsion layer) Silver iodobromide emulsion D Silver 0.40 ExS-7 7.4x10 ^{-4 ExC-7 7.0 × 10 -3} ExY-2 0.0 0 ExY-3 0.10 HBS-1 0.050 Gelatin 0.78 13th layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion F silver ^{1.00 ExS-7 4.0 × 10 -4} ExY- 2 0.10 ExY-3 0.10 HBS-1 0.070 Gelatin 0.86 14th layer (1st protective layer) Silver iodobromide emulsion G Silver 0.20 UV-4 0.11 UV-5 0. 17 HBS-1 5.0 × 10 ^-2 gelatin 1.00 Fifteenth layer (second protective layer) H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 ( (Diameter 1.7 μm) 0.10 B-3 0.10 S-1 0.20 Gelatin 1.20 Furthermore, storability, processability, pressure resistance, anti-mold,
W-1 for improving antibacterial property, antistatic property and coating property
To W-3, B-4 to B-6, F-1 to F-
17 and iron salts, lead salts, gold salts, platinum salts, iridium salts,
Contains rhodium salt.

Table 5 shows compounds represented by abbreviations and silver iodobromide emulsions A to G below.

[0241]

[Chemical 19]

[0242]

[Chemical 20]

[0243]

[Chemical 21]

[0244]

[Chemical formula 22]

[0245]

[Chemical formula 23]

[0246]

[Chemical formula 24]

[0247]

[Chemical 25]

[0248]

[Chemical formula 26]

[0249]

[Chemical 27]

[0250]

[Chemical 28]

[0251]

[Chemical 29]

[0252]

[Chemical 30]

[0253]

[Chemical 31]

[0254]

[Chemical 32]

[0255]

[Chemical 33]

[0256]

[Table 5] In Table 5, (1) Emulsions A to F were reduction-sensitized at the time of grain preparation using thiourea dioxide and thiosulfonic acid according to the method described in Examples of JP-A-2-191938. (2) Emulsions A to F were subjected to gold sensitization and sulfur sensitization in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate according to the method described in Examples of JP-A-3-237450. Selenium sensitized. (3) For the preparation of tabular grains, low molecular weight gelatin is used according to the examples of JP-A-1-158426. (4) Dislocation lines as described in JP-A-3-237450 have been observed in tabular grains and normal crystal grains having a grain structure using a high voltage electron microscope.

The Em-301 used in the fifth layer is the same as the sensitizing dye used in the process for preparing Em-1-1 in Example 1 from A to ExS-1 2.2 × 10 ^-4 mol / Ag.
Mols, ExS-2 1.3 × 10 ⁻⁵ mol / Ag mol and ExS-32.8 × 10 ⁻⁴ mol / Ag mol.

Em-1 used for the fifth layer of Sample 301
Instead of No. 01, based on the emulsion described in Example 1 shown in Table 6 below, the sensitizing dye was changed in the same manner as described above to prepare Samples 302 to 309.

The color photographic light-sensitive material 301 to
309 was exposed in the same manner as in Example 1 and then processed using an automatic processor by the method described below (until the cumulative replenishment amount of the bleaching solution was 3 times the mother liquor tank capacity).

Processing method Processing time Processing temperature * Replenishment amount Tank capacity Color development 3 minutes 15 seconds 37.8 ℃ 25ml 10 liters Bleach 45 seconds 38 ℃ 5ml 4 liters Bleach fixing (1) 45 seconds 38 ℃ -4 liters Bleach Fixing (2) 45 seconds 38 ℃ 30 ml 4 liters Water wash (1) 20 seconds 38 ℃ −2 liters Water wash (2) 20 seconds 38 ℃ 30 ml 2 liters Stability 20 seconds 38 ℃ 20 ml 2 liters Dry 1 minute 55 ℃ * Replenishment amount is 35 mm width per 1 m length. Each step of bleach-fixing and washing is from (2) to (1).
And the overflow of the bleaching solution was all introduced into the bleach-fixing (2).

In the above processing, the carry-in amount of the bleach-fixing solution to the washing step is 2 m per 1 m of the light-sensitive material having a width of 35 mm.
It was l.

The composition of the treatment liquid used for each treatment is shown below. (Color developer) Mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid 5.0 6.0 Sodium sulfite 4.0 5.0 Potassium carbonate 30.0 37.0 Potassium bromide 1.3 0.5 0.5 Iodine Potassium iodide 1.2 mg-hydroxylamine sulfate 2.0 3.6 4- [N-ethyl-N-β-hydro 4.7 6.2 xylethylamino] -2-methylaniline sulfate Water was added 1 0.0 liter 1.0 liter pH 10.00 10.15 (bleaching solution) Mother liquor (g) Replenishing solution (g) 1,3-diaminopropanetetraacetic acid 144.0 206.0 Ferric ammonium monohydrate 1 , 3-Diaminopropanetetraacetic acid 2.8 4.0 Ammonium bromide 84.0 120.0 Ammonium nitrate 17.5 25.0 Ammonia water (27%) 10.0 1.8 Acetic acid (98%) 5 .1 73.0 Add water 1.0 liter 1.0 liter pH 4.3 3.4 (bleach-fixing solution) Mother liquor (g) Replenisher (g) Ethylenediaminetetraacetic acid 50.0-ferric ammonium Dihydrate Ethylenediaminetetraacetic acid 5.0 25.0 Disodium salt Ammonium sulfite 12.0 20.0 Ammonium thiosulfate aqueous solution 290.0 ml 320.0 ml (700 g / liter) Ammonia water (27%) 6.0 ml 15.0 ml Water 1.0 liter 1.0 liter pH 6.8 8.0 (washing water) Common for mother liquor and replenisher Tap water was used as an H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas). , OH type strongly basic anion exchange resin (the same Amberlite IRA-4
(00) is passed through a mixed bed type column to treat calcium and magnesium ions at a concentration of 3 mg / liter or less, and subsequently, 20 mg / liter of sodium diisocyanurate dichloride and 150 mg / liter of sodium sulfate are added to this liquid. did. The pH of this liquid was in the range of 6.5-7.5. (Stabilizer) Common to mother liquor and replenisher (unit: g) Formalin (37%) 1.2 ml Surfactant 0.4 [C ₁₀ H ₂₁ -O- (CH ₂ CH ₂ O) ₁₀ -H] Ethylene glycol 1. 0 Water was added to 1.0 liter pH 5.0-7.0 The sensitivity of each sample was given as the relative value of the reciprocal of the exposure amount which gave the fog density and 0.1 higher than the fog density for the characteristic curve of the cyan color image. Indicated by.

Regarding this sensitivity, samples 301 and 304
And the sensitivity of 307 were set to 100, and the relative value was evaluated.

Further, these samples were stored in an atmosphere of 40 ° C. and 40% RH for 30 days and then evaluated in the same manner as above. The results are also shown in Table 6 below.

[0265]

[Table 6] From Table 6, it is clear that the light-sensitive material of the present invention is a tabular emulsion having a small variation in performance depending on the storage conditions of the seed crystal emulsion, high sensitivity, and improved storage stability.

[0266]

As described in detail above, according to the present invention,
A tabular silver halide emulsion having greatly improved stability in the preparation process is provided, and further, a photographic light-sensitive material having high sensitivity and excellent storage stability is provided by using the emulsion.

Claims (10)

[Claims] 1. A method for preparing a seed crystal emulsion, which comprises using at least one kind of an oxidizing agent for silver. 2. A method for preparing a seed crystal emulsion, which comprises using at least one compound represented by the following general formula (I), (II) or (III). [Chemical 1] In the formula, R, R ¹ and R ² may be the same or different,
It represents an aliphatic group, an aromatic group, or a heterocyclic group, and M represents a cation. L represents a divalent linked value, and m is 0 or 1. The compounds of the general formulas (I) to (III) may be polymers containing a divalent group derived from the structure represented by (I) to (III) as a repeating unit. Also,
When possible, R, R ¹ , R ² and L may combine with each other to form a ring. 3. A silver halide emulsion prepared by using desalted silver halide grains as a seed crystal emulsion, wherein at least one oxidizing agent for silver is used during the step of preparing the seed crystal emulsion. A silver halide emulsion characterized by using. 4. A silver halide emulsion prepared by using desalted silver halide grains as a seed crystal emulsion, wherein a silver halide emulsion represented by the following general formula (I ), (II) or (III), at least one compound is used. [Chemical 2] In the formula, R, R ¹ and R ² may be the same or different,
It represents an aliphatic group, an aromatic group, or a heterocyclic group, and M represents a cation. L represents a divalent linking group, and m is 0 or 1. The compounds of the general formulas (I) to (III) may be polymers containing a divalent group derived from the structure represented by (I) to (III) as a repeating unit. Also,
When possible, R, R ¹ , R ² and L may combine with each other to form a ring. 5. The tabular silver halide grains having an aspect ratio of 2 or more have a projected area of 50 to 10 of the total silver halide grains.
Aspect ratio 3 prepared by using as a seed crystal emulsion after desalting a silver halide emulsion occupying 0%
The tabular silver halide grains described above are silver halide emulsions occupying 50 to 100% of the projected area of all silver halide grains, and at least one oxidizer for silver is used during the step of preparing the seed crystal emulsion. A silver halide emulsion characterized by using. 6. The tabular silver halide grains having an aspect ratio of 2 or more have a projected area of 50 to 10 of the total silver halide grains.
Aspect ratio 3 prepared by using as a seed crystal emulsion after desalting a silver halide emulsion occupying 0%
The tabular silver halide grains described above are silver halide emulsions occupying 50 to 100% of the projected area of all silver halide grains, and are represented by the general formula (I) shown below during the step of preparing the seed crystal emulsion. A silver halide emulsion containing at least one compound represented by formula (II), or (III). [Chemical 3] In the formula, R, R ¹ and R ² may be the same or different and each represents an aliphatic group, an aromatic group, or a heterocyclic group, and M represents a cation. L represents a divalent linking group, and m is 0 or 1. The compounds of the general formulas (I) to (III) may be polymers containing a divalent group derived from the structure represented by (I) to (III) as a repeating unit. Further, if possible, R, R ¹ , R ² and L may be bonded to each other to form a ring. 7. A photographic light-sensitive material having at least one silver halide emulsion layer containing the silver halide emulsion according to claim 3 on a support. 8. A photographic light-sensitive material having at least one silver halide emulsion layer containing the silver halide emulsion according to claim 4 on a support. 9. A photographic light-sensitive material having at least one silver halide emulsion layer containing the silver halide emulsion according to claim 5 on a support. 10. A photographic light-sensitive material having at least one silver halide emulsion layer containing the silver halide emulsion according to claim 6 on a support.